CN104183719A - Inverted organic light emission diode and preparation method thereof - Google Patents
Inverted organic light emission diode and preparation method thereof Download PDFInfo
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- CN104183719A CN104183719A CN201310193562.8A CN201310193562A CN104183719A CN 104183719 A CN104183719 A CN 104183719A CN 201310193562 A CN201310193562 A CN 201310193562A CN 104183719 A CN104183719 A CN 104183719A
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Abstract
The invention discloses an inverted organic light emission diode and a preparation method thereof. The inverted organic light emission diode comprises a substrate, a cathode layer, an organic function layer, a PN node and an anode layer which are sequentially stacked. The organic function layer comprises a light-emitting layer; a P-type semiconductor layer of the PN node is in stack combination with the cathode layer; and an N-type semiconductor layer of the PN node is in stack combination with the organic function layer, wherein the P-type semiconductor layer is made of phthalocyanine compounds, and the N-type semiconductor layer is made of fullerene materials. The preparation method comprises evaporating the PN node and the organic function layer on the outer surface of the cathode layer sequentially. The inverted organic light emission diode is high in luminous efficiency, low in starting voltage, simple in process, easy to control conditions, high in qualified rate of finished products, improved in production efficiency, reduced in production cost, and is suitable for industrialized production.
Description
Technical field
The invention belongs to electric light source technology field, relate to specifically a kind of inversion organic electroluminescence 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.
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, and for example light-emitting device, inverted type light-emitting device are launched in top.For the inversion type OLED light-emitting device of lower bright dipping, conventionally need a high transparent electrode as negative electrode, conventional transparent conductive oxide film is as negative electrode at present, although its transmitance is high, but because its work content is higher, unfavorable to the injection of electronics, make the light efficiency of device be difficult to improve.。
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of and can effectively solve electronic injection difficulty, and the high inversion Organnic electroluminescent device of luminous efficiency.
Another object of the present invention is to provide a kind of technique to be simply inverted Organnic electroluminescent device preparation method.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of inversion Organnic electroluminescent device, comprise the substrate, cathode layer, organic function layer and the anode layer that stack gradually combination, described organic function layer comprises luminescent layer, also covering is folded is combined in the PN junction between described cathode layer and organic function layer for described inversion Organnic electroluminescent device, 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 phthalocyanine compound is at least one in CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc, phthalocyanine platinum; Described N type semiconductor layer material is fullerene-based material, and described fullerene-based material is at least one in carbon 60, carbon 70.
And the preparation method of above-mentioned inversion Organnic electroluminescent device, comprises the steps:
In vacuum coating system, phthalocyanine compound evaporation is prepared to p type semiconductor layer at cathode layer outer surface;
In vacuum coating system, fullerene-based material evaporation is prepared to n type semiconductor layer at described p type semiconductor layer outer surface, described n type semiconductor layer and described p type semiconductor layer form PN junction.
Above-mentioned inversion Organnic electroluminescent device arranges PN junction between cathode layer and organic function layer, under the effect of electric field externally, interface formation separation of charge at 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, thereby the negative electrode efficiently solving as light-emitting area causes the technical problem of electronic injection difficulty because work content is high, and gives the luminous efficiency that this inversion Organnic electroluminescent 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 inversion Organnic electroluminescent device is having cathode layer outer surface to prepare successively p type semiconductor layer and n type semiconductor layer formation PN junction by evaporation coating method, 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.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention is inverted Organnic electroluminescent device structural representation;
Fig. 2 is the schematic flow sheet that the embodiment of the present invention is inverted Organnic electroluminescent device preparation method;
Fig. 3 is the inversion Organnic electroluminescent device of embodiment 1 preparation and the voltage-to-current density characteristic curve figure of the device that comparison example is made.
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 inversion Organnic electroluminescent device of luminous efficiency, and its structure as shown in Figure 1.This inversion Organnic electroluminescent device comprises substrate 1, cathode layer 2, PN junction 3, organic function layer 4 and the anode layer 5 that stacks gradually combination.
Particularly, the material of aforesaid substrate 1 is transparent glass, transparent polymer film material etc., as the flexibility of preparing with polymer thin-film material substrate is inverted OLED device.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 cathode material of above-mentioned cathode 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 inversion Organnic electroluminescent device, and in addition, this preferred transparent conductive oxide electric conductivity is excellent.These cathode layer 6 thickness are preferably 70～200nm, are preferably 100nm.
The setting of above-mentioned PN junction 3, under the effect of electric field externally, interface formation separation of charge at PN junction layer 3, hole is moved to cathode layer 2, electronics moves to organic function layer 4, make in electronic injection organic function layer 4 and to arrive luminescent layer 42 excitation light-emitting materials luminous, thereby the negative electrode efficiently solving as light-emitting area cause the technical problem of electronic injection difficulty because work content is high.Therefore, the embodiment of the present invention that is arranged so that of PN junction 3 is inverted Organnic electroluminescent device and is had high luminance, meanwhile, because PN junction 3 has reduced electronic injection difficulty, therefore, effectively reduces the starting resistor that the present invention is inverted Organnic electroluminescent device.This PN junction 3 consists of with n type semiconductor layer 32 p type semiconductor layer 31 of mutual stacked combination, p type semiconductor layer 31 and the stacked combination of cathode layer 2, and n type semiconductor layer 32 and the stacked combination of organic function layer 4.
In specific embodiment, p type semiconductor layer 31 materials in this PN junction 3 are phthalocyanine compound.This phthalocyanine compound is preferably metal phthalocyanine compound, for example but be not only CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), and at least one in phthalocyanine platinum (PtPc).In a preferred embodiment, the thickness of p type semiconductor layer 31 is 1nm～20nm, and in this thickness range, p type semiconductor layer 31 can obtain best hole migration effect.
N type semiconductor layer 32 materials in this PN junction 3 are fullerene-based material.This fullerene-based material is preferably at least one in carbon 60, carbon 70.This preferred fullerene-based material can be prepared tunic with technique for vacuum coating, has excellent stability, makes n type semiconductor layer 32 firm with p type semiconductor layer 31 combinations, is not easy to produce the phenomenon of phase-splitting.In a preferred embodiment, the thickness of n type semiconductor layer 32 is 1nm～20nm, and in this thickness range, n type semiconductor layer 32 can obtain best electron transfer effect.
Above-mentioned organic function layer 4 comprises electron transfer layer 41, luminescent layer 42, the hole transmission layer 43 that stacks gradually combination, and electron transfer layer 41 and the stacked combination in the relative surface of face that combines with cathode layer 2 of PN junction 3 be the stacked combination of n type semiconductor layer 32 with PN junction 3, the stacked combination in arbitrary surface of hole transmission layer 43 and anode layer 5, as shown in Figure 1.
In specific embodiment, the selected material of electron transfer layer 41 in this organic function layer 4 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 41 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 specific embodiment, the selected material of luminescent layer 42 in this organic function layer 4 can be guest materials and material of main part dopant mixture or phosphor material.These luminescent layer 42 thickness are 1～20nm.Certainly, these luminescent layer 42 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 42 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).
When luminescent layer 42 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 selected material of hole transmission layer 43 in this organic function layer 4 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 43 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 further preferred embodiment, on the basis of organic function layer 4 as shown in Figure 1, above-mentioned organic function layer 4 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 5 and hole transmission layer 43.
Particularly, the selected material of hole injection layer can be hole-injecting material, as WO
3, VO
x, WO
xor MoO
3in at least one, 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.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 of 5 of itself and anode layers, has strengthened electric conductivity, improves the hole injectability of anode layer 5 ends.
In further preferred embodiment, on the basis of organic function layer 4 as shown in Figure 1, above-mentioned organic function layer 4 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 43 and luminescent layer 42, and hole blocking layer is stacked to be combined between luminescent layer 42 and electron transfer layer 41.The setting of this electronic barrier layer and hole blocking layer, can respectively electronics and hole be trapped in luminescent layer 42 as much as possible, to improve hole and electronics meeting rate in luminescent layer 42, 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 42.As electronic barrier layer can will be trapped in luminescent layer 42 as much as possible from cathode layer 2 injected electrons, hole blocking layer can will be trapped in luminescent layer 42 as much as possible from anode layer 5 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.
Above-mentioned anode layer 5 materials can be selected metal, as one or more the alloy in Ag, Al, Au, Pt etc.The thickness of anode layer 5 can but be not only 70～200nm.Certainly, anode layer 5 can also be other anode materials well known in the art, and its thickness also can adopt the conventional thickness in this area.
From the above, above-mentioned inversion Organnic electroluminescent device arranges PN junction layer 3 between organic function layer 4 and cathode layer 2, under the effect of electric field externally, interface formation separation of charge at PN junction layer 3, hole is moved to cathode layer 2, electronics moves to organic function layer 4, make in electronic injection organic function layer 4 and to arrive luminescent layer 42 excitation light-emitting materials luminous, thereby the negative electrode efficiently solving as light-emitting area causes the technical problem of electronic injection difficulty because work content is high, improved the high luminance of this inversion Organnic electroluminescent device.Meanwhile, effectively reduce the starting resistor that the embodiment of the present invention is inverted Organnic electroluminescent device.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method who is inverted Organnic electroluminescent device above.So the method process chart shows as Fig. 2, simultaneously referring to Fig. 1, the method comprises the steps:
S01., substrate 1 is provided;
S02. prepare cathode layer 2: in vacuum coating system, at the substrate 1 one plated surface cathode layers 2 of step S01;
S03. prepare PN junction 3:
In vacuum coating system, phthalocyanine compound evaporation is prepared to p type semiconductor layer 31 at cathode layer 2 outer surfaces;
In vacuum coating system, fullerene-based material evaporation is prepared to n type semiconductor layer 32 at p type semiconductor layer 31 outer surfaces, this p type semiconductor layer 31 forms PN junction 3 with n type semiconductor layer 32;
S04. prepare organic function layer 4: that at step S03, prepares n type semiconductor layer 32 plates each functional layer of machine functional layer 4 successively with the p type semiconductor layer 31 relative surface of face that combines, and forms organic function layer 4; S05. prepare anode layer 5: in vacuum systems, organic function layer 4 outer surfaces that anode material evaporation is prepared at step S04 are prepared anode layer 5.
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, in vacuum systems, transparent conductive oxide and cathode layer 2 thickness all as described above, do not repeat them here.Preferably, to become the sputtering technology condition of cathode layer 2 be that 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, preparing the process conditions of cathode layer 2 also can be according to existing processing parameter setting.
In above-mentioned steps S03, the preferred thickness of the preferred kind of phthalocyanine compound and fullerene-based material, p type semiconductor layer 31 and n type semiconductor layer 32 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 p type semiconductor layer 31 and the involved process conditions of n type semiconductor layer 32
-5～1 * 10
-3pa, the evaporation rate of phthalocyanine compound is 0.1～1nm/s, the evaporation rate of fullerene-based material is 0.01～1nm/s.
In above-mentioned steps S04, when organic function layer 4 as described above, when it comprises electron transfer layer 41, luminescent layer 42, the hole transmission layer 43 that stacks gradually combination, the method for therefore preparing organic function layer 4 is at n type semiconductor layer 32 outer surfaces successively evaporation electron transfer layer 41, luminescent layer 42, hole transmission layer 43;
When organic function layer 4 as described above, it comprises the electron transfer layer 41 that stacks gradually combination, luminescent layer 42, hole transmission layer 43, hole injection layer, or comprise the electron transfer layer 41 that stacks gradually combination, hole blocking layer, luminescent layer 42, electronic barrier layer, hole transmission layer 43, during hole injection layer, the method of preparing organic function layer 3 is at n type semiconductor layer 32 outer surfaces successively evaporation electron transfer layer 41, luminescent layer 42, hole transmission layer 43, hole injection layer, or evaporation electron transfer layer 41 successively, hole blocking layer, luminescent layer 42, electronic barrier layer, hole transmission layer 43, hole injection layer, form organic function layer 4.
Wherein, plate this each layer 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 organic function layer 4 each layer process conditions also can carry out according to existing processing parameter setting.
In above-mentioned steps S05, evaporation anode layer 5, its evaporation condition adopts the process conditions of this area routine.Wherein, the thickness of the anode material that evaporation anode layer 5 is used and the anode layer 5 preparing all as described above, does not repeat them here.While steaming anode layer 5, 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 5 also can be carried out according to existing processing parameter setting.
From the above, the preparation method of above-mentioned inversion Organnic electroluminescent device prepares respectively PN junction 3, organic function layer 4 and anode layer 5 by evaporation and sputtering method successively at cathode 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, the embodiment of the present invention is inverted to organic electroluminescence device and preparation method thereof and is further elaborated.
Embodiment 1
An inversion Organnic electroluminescent device, its structure is: glass substrate/ITO/CuPc/C60/Bphen/Ir (ppy)
3and CBP/NPB/Ag.
This inversion Organnic electroluminescent device is preparation method comprise the following steps:
A) 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;
B) preparation of cathode layer: in vacuum coating system, the glass baseplate surface with ITO in step a) is prepared transparent conductive oxide film by magnetron sputtering, thickness is 100nm, the base vacuum degree of magnetron sputtering is 1 * 10
-5pa, forms negative electrode;
C) preparation of PN junction: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, by thermal evaporation techniques, evaporation rate is
, the cathode outer surface with CuPc in step b) is prepared P layer, and thickness is 5nm; And then by thermal evaporation techniques, evaporation rate is
, with C60, at the outer surface of P layer, prepare N layer, thickness is 1nm;
D) preparation of organic function layer: the N layer outer surface in step b) prepared electron transfer layer, luminescent layer, hole transmission layer successively; Particularly,
The preparation of electron transfer layer: adopt Bphen as electric transmission layer material, vacuum degree is 1 * 10
-5pa, evaporation rate
, evaporation thickness 30nm; The preparation of luminescent layer: by the Ir of 1 part of quality (ppy)
3be doped in the CBP of 10 parts of quality, vacuum degree is 1 * 10
-5pa, evaporation rate
, evaporation thickness 10nm; The preparation of hole transmission layer: adopt NPB as hole transmission layer, vacuum degree is 1 * 10
-5pa, evaporation rate
, evaporation thickness 30nm;
E) making of anode layer: utilize thermal evaporation or electron beam evaporation technique, adopt Ag as anode layer material, the organic function layer outer surface in step d) is prepared anode layer, thickness 100nm, vacuum degree is 1 * 10
-5pa, evaporation rate
.
Embodiment 2
An inversion Organnic electroluminescent device, its structure is: glass substrate/AZO/ZnPc/C70/TPBi/Ir (piq)
3and NPB/2-TNATA/Al.
This inversion Organnic electroluminescent device is preparation method comprise the following steps:
A) glass substrate pre-treatment: washed with de-ionized water → isopropyl alcohol cleaning → acetone cleans, and all cleans with supersonic wave cleaning machine, and scavenging period is 20 minutes, then dries up with nitrogen;
B) preparation of cathode layer: in vacuum coating system, the glass baseplate surface with AZO in step a) is prepared transparent conductive oxide film by magnetron sputtering, thickness is 70nm, the base vacuum degree of magnetron sputtering is 1 * 10
-3pa, forms negative electrode;
C) preparation of PN junction: be 1 * 10 in vacuum degree
-3in the vacuum coating system of Pa, by thermal evaporation techniques, evaporation rate is
, the cathode outer surface with ZnPc in step b) is prepared P layer, and thickness is 1nm; And then by thermal evaporation techniques, evaporation rate is
, with C70, at the outer surface of P layer, prepare N layer, thickness is 5nm;
D) preparation of organic function layer: the N layer outer surface in step b) prepared electron transfer layer, luminescent layer, hole transmission layer successively; Particularly,
The preparation of electron transfer layer: adopt TPBi as electric transmission layer material, vacuum degree is 1 * 10
-3pa, evaporation rate
, evaporation thickness 60nm; The preparation of luminescent layer: by the Ir of 8 parts of quality (piq)
3be doped in the NPB of 100 parts of quality, vacuum degree is 1 * 10
-3pa, evaporation rate
, evaporation thickness 20nm; The preparation of hole transmission layer: adopt 2-TNATA as hole transmission layer, vacuum degree is 1 * 10
-3pa, evaporation rate
, evaporation thickness 60nm;
E) making of anode layer: utilize thermal evaporation or electron beam evaporation technique, adopt Al as anode layer material, the organic function layer outer surface in step d) is prepared anode layer, thickness 70nm, vacuum degree is 1 * 10
-3pa, evaporation rate
.
Embodiment 3
An inversion Organnic electroluminescent device, its structure is: glass substrate/GZO/VOPc/C60 and C70/PBD/DCJTB and Alq
3/ m-MTDATA/Au.
This inversion Organnic electroluminescent device is preparation method comprise the following steps:
A) glass substrate pre-treatment: washed with de-ionized water → isopropyl alcohol cleaning → acetone cleans, and all cleans with supersonic wave cleaning machine, and scavenging period is 20 minutes, then dries up with nitrogen;
B) preparation of cathode layer: in vacuum coating system, the glass baseplate surface with GZO in step a) is prepared transparent conductive oxide film by magnetron sputtering, thickness is 200nm, the base vacuum degree of magnetron sputtering is 5 * 10
-4pa, forms negative electrode;
C) preparation of PN junction: be 5 * 10 in vacuum degree
-4in the vacuum coating system of Pa, by thermal evaporation techniques, evaporation rate is
, the cathode outer surface with VOPc in step b) is prepared P layer, and thickness is 10nm; The C60:C70 that is 1:1 by mass ratio doping steams work altogether, at the outer surface of P layer, prepares N layer, and thickness is 15nm, and evaporation rate is
;
D) preparation of organic function layer: the N layer outer surface in step b) prepared electron transfer layer, luminescent layer, hole transmission layer successively; Particularly,
The preparation of electron transfer layer: adopt PBD as electric transmission layer material, vacuum degree is 5 * 10
-4pa, evaporation rate
, evaporation thickness 20nm; The preparation of luminescent layer: the Alq that the DCJTB of 1 part of quality is doped into 100 parts of quality
3in, vacuum degree is 5 * 10
-4pa, evaporation rate
, evaporation thickness 1nm; The preparation of hole transmission layer: adopt m-MTDATA as hole transmission layer, vacuum degree is 5 * 10
-4pa, evaporation rate
, evaporation thickness 20nm;
E) making of anode layer: utilize thermal evaporation or electron beam evaporation technique, adopt Au as anode layer material, the organic function layer outer surface in step d) is prepared anode layer, thickness 200nm, vacuum degree is 5 * 10
-4pa, evaporation rate
.
Embodiment 4
An inversion Organnic electroluminescent device, its structure is: glass substrate/IZO/TiOPc/C60 and C70/BCP/Rubrene/TPD/Pt.
This inversion Organnic electroluminescent device is preparation method comprise the following steps:
A) glass substrate pre-treatment: washed with de-ionized water → isopropyl alcohol cleaning → acetone cleans, and all cleans with supersonic wave cleaning machine, and scavenging period is 20 minutes, then dries up with nitrogen;
B) preparation of cathode layer: in vacuum coating system, the glass baseplate surface with IZO in step a) is prepared transparent conductive oxide film by magnetron sputtering, thickness is 100nm, the base vacuum degree of magnetron sputtering is 1 * 10
-5pa, forms negative electrode;
C) preparation of PN junction: be 1 * 10 in vacuum degree
-5in the vacuum coating system of Pa, by thermal evaporation techniques, evaporation rate is
, the cathode outer surface with TiOPc in step b) is prepared P layer, and thickness is 20nm; The C60:C70 that is 1:4 by mass ratio doping steams work altogether, at the outer surface of P layer, prepares N layer, and thickness is 20nm, and evaporation rate is
;
D) preparation of organic function layer: the N layer outer surface in step b) prepared electron transfer layer, luminescent layer, hole transmission layer successively; Particularly,
The preparation of electron transfer layer: adopt BCP as electric transmission layer material, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 30nm; The preparation of luminescent layer: adopt Rubrene as luminescent layer material, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 10nm; The preparation of hole transmission layer: adopt TPD as hole transmission layer, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 40nm;
E) making of anode layer: utilize thermal evaporation or electron beam evaporation technique, adopt Pt as anode layer material, the organic function layer outer surface in step d) is prepared anode layer, thickness 70nm, vacuum degree is 1 * 10
-5pa, evaporation rate
Embodiment 5
An inversion Organnic electroluminescent device, its structure is: glass substrate/IZO/PtPc/C60 and C70/TAZ/DPVBi/TCTA/Ag.
This inversion Organnic electroluminescent device is preparation method comprise the following steps:
A) glass substrate pre-treatment: washed with de-ionized water → isopropyl alcohol cleaning → acetone cleans, and all cleans with supersonic wave cleaning machine, and scavenging period is 20 minutes, then dries up with nitrogen;
B) preparation of cathode layer: in vacuum coating system, the glass baseplate surface with IZO in step a) is prepared transparent conductive oxide film by magnetron sputtering, thickness is 100nm, the base vacuum degree of magnetron sputtering is 1 * 10
-5pa, forms negative electrode;
C) preparation of PN junction: be 1 * 10 in vacuum degree
-5in the vacuum coating system of Pa, by thermal evaporation techniques, evaporation rate is
cathode outer surface with PtPc in step b) is prepared P layer, and thickness is 15nm; The C60:C70 that is 3:2 by mass ratio doping steams work altogether, at the outer surface of P layer, prepares N layer, and thickness is 10nm, and evaporation rate is
D) preparation of organic function layer: the N layer outer surface in step b) prepared electron transfer layer, luminescent layer, hole transmission layer successively; Particularly,
The preparation of electron transfer layer: adopt TAZ as electric transmission layer material, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 30nm; The preparation of luminescent layer: adopt DPVBi as luminescent layer material, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 10nm; The preparation of hole transmission layer: adopt TCTA as hole transmission layer, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 35nm;
E) making of anode layer: utilize thermal evaporation or electron beam evaporation technique, adopt Ag as anode layer material, the organic function layer outer surface in step d) is prepared anode layer, thickness 100nm, vacuum degree is 1 * 10
-5pa, evaporation rate
Comparison example
An inversion Organnic electroluminescent device, its structure is: glass substrate/ITO/Bphen/Ir (ppy)
3and CBP/NPB/Ag.
This inversion Organnic electroluminescent device is preparation method comprise the following steps:
A) glass substrate pre-treatment: washed with de-ionized water → isopropyl alcohol cleaning → acetone cleans, and all cleans with supersonic wave cleaning machine, and scavenging period is 20 minutes, then dries up with nitrogen;
B) preparation of cathode layer: in vacuum coating system, the glass baseplate surface with ITO in step a) is prepared transparent conductive oxide film by magnetron sputtering, thickness is 100nm, the base vacuum degree of magnetron sputtering is 1 * 10
-5pa, forms negative electrode;
C) preparation of organic function layer: the N layer outer surface in step b) prepared electron transfer layer, luminescent layer, hole transmission layer successively; Particularly,
The preparation of electron transfer layer: adopt Bphen as electric transmission layer material, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 30nm; The preparation of luminescent layer: the Ir (ppy) that adopts 1 part of quality
3make luminescent layer material with the CBP doping evaporation of 10 parts of quality, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 10nm; The preparation of hole transmission layer: adopt NPB as hole transmission layer, vacuum degree is 1 * 10
-5pa, evaporation rate
evaporation thickness 30nm;
D) making of anode layer: utilize thermal evaporation or electron beam evaporation technique, adopt Ag as anode layer material, the organic function layer outer surface in step d) is prepared anode layer, thickness 100nm, vacuum degree is 1 * 10
-5pa, evaporation rate
Be inverted Organnic electroluminescent device and carry out correlated performance test
Inversion Organnic electroluminescent device prepared by above-described embodiment 1 to embodiment 5 and comparison example 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
| ? | Starting resistor | Luminous efficiency (lm/W) |
| Embodiment 1 | 2.8 | 15.9 |
| Embodiment 2 | 2.7 | 14.6 |
| Embodiment 3 | 2.7 | 12.3 |
| Embodiment 4 | 2.7 | 11.1 |
| Embodiment 5 | 2.9 | 10.7 |
| Comparative example 1 | 3.6 | 9.8 |
Data by the embodiment 1 to embodiment 5 in table 1 and comparative example are known: compare with common luminescent device, inversion Organnic electroluminescent device prepared by the embodiment of the present invention is owing to having adopted a PN junction structure, the injection barrier of electronics is reduced, therefore can improve the injection efficiency of electronics, therefore obtain lower starting resistor, and adopted the electrode of transparent conductive oxide as bright dipping, so the light extraction efficiency of device is high, thereby obtains higher light efficiency.
In addition, the voltage-to-current density of inversion Organnic electroluminescent device prepared by the test embodiment of the present invention 1 and comparative example, and describe curve chart, as shown in Figure 2: the inversion Organnic electroluminescent device that the embodiment of the present invention 1 is prepared with comparative example is under identical driving voltage, because the electronic injection of embodiment 1 is more prone to, and the electronic injection of comparative example is difficult, therefore at identical driving voltage, compares, embodiment 1 has higher Injection Current, thereby can obtain higher luminous efficiency.
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 (8)
1. be inverted Organnic electroluminescent device for one kind, comprise the substrate, cathode layer, organic function layer and the anode layer that stack gradually combination, described organic function layer comprises luminescent layer, it is characterized in that: also comprise the stacked PN junction being combined between described cathode layer and organic function layer, 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 phthalocyanine compound is at least one in CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc, phthalocyanine platinum; Described N type semiconductor layer material is fullerene-based material, and described fullerene-based material is at least one in carbon 60, carbon 70.
2. inversion Organnic electroluminescent device as claimed in claim 1, is characterized in that: the thickness of described p type semiconductor layer is 1nm～20nm.
3. inversion Organnic electroluminescent device as claimed in claim 1, is characterized in that: the thickness of described n type semiconductor layer is 1nm～20nm.
4. a preparation method who is inverted Organnic electroluminescent device, comprises the steps:
In vacuum coating system, phthalocyanine compound evaporation is prepared to p type semiconductor layer at described cathode layer outer surface;
In vacuum coating system, fullerene-based material evaporation is prepared to n type semiconductor layer at described p type semiconductor layer outer surface, described n type semiconductor layer and described p type semiconductor layer form PN junction.
5. the preparation method of inversion Organnic electroluminescent device as claimed in claim 4, is characterized in that: in the step of the described p type semiconductor layer of preparation, vacuum degree during described evaporation is 1 * 10
-5pa～1 * 10
-3pa, described phthalocyanine compound evaporation rate is
6. the preparation method of inversion organic electroluminescence device as claimed in claim 4, is characterized in that: in the step of the described n type semiconductor layer of preparation, vacuum degree during described evaporation is 1 * 10
-5pa～1 * 10
-3pa, described fullerene-based material evaporation rate is
7. the preparation method of the inversion Organnic electroluminescent device as described in as arbitrary in claim 4～6, is characterized in that: described phthalocyanine compound comprises at least one in CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc, phthalocyanine platinum.
8. the preparation method of the inversion Organnic electroluminescent device as described in as arbitrary in claim 4～6, is characterized in that: described fullerene-based material is at least one in carbon 60, carbon 70.
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| WO2018113237A1 (en) * | 2016-12-23 | 2018-06-28 | 京东方科技集团股份有限公司 | Organic electroluminescent display panel and manufacturing method therefor, and display apparatus |
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