CN104183769A - Organic light emitting diode and preparation method thereof - Google Patents
Organic light emitting diode and preparation method thereof Download PDFInfo
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- CN104183769A CN104183769A CN201310194291.8A CN201310194291A CN104183769A CN 104183769 A CN104183769 A CN 104183769A CN 201310194291 A CN201310194291 A CN 201310194291A CN 104183769 A CN104183769 A CN 104183769A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
The invention provides an organic light emitting diode and a preparation method thereof. The invention discloses an organic light emitting diode which is characterized in that a buffer layer is arranged between a glass substrate and an anode; and the other side of the glass substrate is provided with a protection layer. The buffer layer comprises a poly-p-xylylene film and an inorganic film which are stacked alternatively, wherein the inorganic film of the buffer layer is silicon dioxide or aluminium oxide. The protection layer comprises a poly-p-xylylene film and an inorganic film which are stacked alternatively, wherein the inorganic film of the protection layer is silicon dioxide or aluminium oxide. The two sides of the glass substrate are respectively provided with the protective layer and the buffer layer which play protection effect on the glass, so that the surface of the glass is not damaged by external materials, and stress produced when the glass surface bends can be well dispersed; and a layer of inorganic oxide serving as buffer is added between the anode and the poly-p-xylylene film, so that the adhesive force between the two can be improved.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emitting Diode, hereinafter to be referred as OLED), have that brightness is high, material range of choice is wide, driving voltage is low, entirely solidify the characteristics such as active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be 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, be current lot of domestic and foreign researcher's focal point.
The heat resistance of thin polymer film is not good enough, and excellent not to stopping of water oxygen performance, be unfavorable for the device raising in useful life, and foil surfaces roughness is high, need to carry out some medal polishs processing and could prepare OLED device, and it can only prepare the OLED device of top transmitting.In the OLED of prior art device, the OLED device that uses glass substrate to make does not possess bending feature, and Glass breadks easily, and the application of luminescent device has been caused to impact.When the thickness of glass substrate is during at 50～200 μ m, be commonly referred to ultra-thin glass, ultra-thin glass has flexibility, and possesses and have the light transmission of glass and the barrier of sheet metal, but the toughness of ultra-thin glass is not good, character is more crisp, be applied to OLED device in the time that deflection is used, ultra-thin glass can destroy, and produces slight crack, device performance is declined, cause component failure.For flexible OLED product, if use traditional OLED encapsulation technology, add encapsulation cover plate in device back, can produce the problems such as weight is large, cost is high, bad mechanical strength, limit the performance performance of flexible OLED product.At present, the waterproof oxygen of most flexible OLED is indifferent, and useful life is shorter, and complicated process of preparation, cost are high.
Summary of the invention
In order to address the above problem, the present invention aim to provide a kind of photochromic stable, waterproof oxygen ability is strong, long organic electroluminescence devices of life-span.The present invention also provides a kind of preparation method of organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, anode, functional layer and negative electrode are cascading in glass substrate, at described cathode surface, encapsulated layer is set, make to form enclosure space between glass substrate and encapsulated layer, described anode, functional layer and negative electrode are contained in described enclosure space, between described glass substrate and anode, are provided with resilient coating, are provided with protective layer at the another side of described glass substrate;
Described resilient coating comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described resilient coating is silicon dioxide or aluminium oxide; Described protective layer comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described protective layer is silicon dioxide or aluminium oxide.
Preferably, glass substrate is ultra-thin glass.Ultra-thin glass not only has the light transmission of glass, also has the barrier of flexibility and sheet metal.
Preferably, the thickness of glass substrate is 50～200 μ m.
Preferably, glass substrate is greater than 80% to the transmitance of visible ray.
Glass substrate comprises two faces that are oppositely arranged, and resilient coating and protective layer lay respectively on two faces.Wherein, resilient coating is arranged between glass substrate and anode, comprises alternately laminated parylene film and inorganic matter film; Protective layer is arranged on the another side of glass substrate, comprises alternately laminated parylene film and inorganic matter film.
Organic thin film has good pliability; its impact resistance is far above glass material; therefore the two sides being oppositely arranged in glass substrate all arranges parylene film can have good protective effect to glass; make its in use easy fracture not; improve overall toughness; and Parylene filming performance is good, the stress that can disperse well glass surface to produce in the time of deflection.In addition, parylene film has the transmitance very high in visible region, is beneficial to the bright dipping of device.
Preferably, the thickness of parylene film is 1～10 μ m.
The inorganic matter film of protective layer is arranged on parylene film, can play the effect of protection parylene film, makes it not by exterior material deface, thereby has ensured the protective value of parylene film to glass.
The inorganic matter film of resilient coating is arranged between parylene film and anode, because the thermal coefficient of expansion of the anode materials such as Parylene and tin indium oxide (ITO) differs far away, therefore between anode and parylene film, add one deck inorganic oxide as buffering, can improve adhesive force between the two.Meanwhile, this inorganic matter film can be protected parylene film, makes it not by exterior material deface, thereby has ensured the protective value of parylene film to glass.
Inorganic matter film in protective layer is silicon dioxide or aluminium oxide.
Preferably, the thickness of the inorganic matter film in protective layer is 1～10 μ m.
Inorganic matter film in resilient coating is silicon dioxide or aluminium oxide.
Preferably, the thickness of the inorganic matter film in resilient coating is 0.2～2 μ m.
Inorganic matter film in inorganic matter film and resilient coating in protective layer can be identical or different material.
Preferably, the inorganic matter film in inorganic matter film and the resilient coating in protective layer is silicon dioxide.
Anode is arranged on resilient coating.
Preferably, the material of anode is tin indium oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO) or gallium oxide zinc (GZO).
Preferably, the thickness of anode is 70～100nm.
Functional layer is arranged on anode, comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Preferably, the material of hole injection layer is CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc) or phthalocyanine platinum (PtPc).
Preferably, the thickness of hole injection layer is 20～40nm.
Preferably, the material of hole transmission layer is 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) or 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).
Preferably, the thickness of hole transmission layer is 20～40nm.
Preferably, the material of luminescent layer is the material of main part doped with guest materials, described guest materials is 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 that iridium (FIrpic), two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid close iridium (FIr6), (acetylacetone,2,4-pentanedione) closes iridium (Ir (MDQ)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) or three (2-phenylpyridines) close iridium (Ir (ppy)
3), described material of main part is 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq
3), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), the doping mass fraction of described guest materials in material of main part is 1%～10%.
Also preferably, the material of luminescent layer is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4, two [4-(di-p-tolyl amino) styryl] biphenyl (DPAVBi) or 5 of 4'-, 6,11,12-tetraphenyl naphthonaphthalene (Rubrene).
Preferably, the thickness of luminescent layer is 1～20nm.
Preferably, the material of electron transfer layer is 2-(4-xenyl)-5-(4-the 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) or 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of electron transfer layer is 20～40nm.
Preferably, the material of electron injecting layer is lithium fluoride (LiF) or cesium fluoride (CsF).
Preferably, the thickness of electron injecting layer is 0.5～1nm.
Preferably, the material of negative electrode is argent (Ag), aluminium (Al), magnesium silver alloy (Mg-Ag) or magnadure (Mg-Al).
Preferably, the thickness of negative electrode is 70～200nm.
Encapsulated layer and glass substrate are connected to form enclosure space, and anode, functional layer and negative electrode are placed in this enclosure space, for the infiltration of block water oxygen.
Preferably, encapsulated layer is alternately laminated silicon dioxide and silicon nitride.
More preferably, encapsulated layer is silicon dioxide and the silicon nitride of alternately laminated 3 times.
Preferably, the thickness of encapsulated layer is 600nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate;
(2) prepare respectively protective layer and resilient coating on the two sides of described glass substrate, described resilient coating comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described resilient coating is silicon dioxide or aluminium oxide; Described protective layer comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described protective layer is silicon dioxide or aluminium oxide:
By paraxylene ring disome thermal cracking, then polymerization forms parylene film in described glass substrate; On described parylene film, inorganic matter film is prepared in sputter, and described inorganic matter film is silicon dioxide, silicon nitride or aluminium oxide, and sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, power density 1～40W/cm
2, sputtering rate 0.2～2nm/s;
(3) on described resilient coating, prepare successively anode, functional layer and negative electrode;
Wherein, described anode is prepared by sputtering method, and functional layer and negative electrode are prepared by thermal resistance evaporation coating method; Described sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, sputtering rate 0.2～2nm/s; Described thermal resistance evaporation condition is pressure 1 × 10
-5～1 × 10
-3pa, evaporation speed is 0.01～2nm/s;
(4) encapsulated layer is arranged on to described cathode surface, makes to form enclosure space between glass substrate and encapsulated layer, described anode, functional layer and negative electrode are contained in described enclosure space, and sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, sputtering rate 0.2～2nm/s;
Finally obtain described organic electroluminescence device.
In step (1), preferably, glass substrate is ultra-thin glass.Ultra-thin glass not only has the light transmission of glass, also has the barrier of flexibility and sheet metal.
Preferably, the thickness of glass substrate is 50～200 μ m.
Preferably, glass substrate is greater than 80% to the transmitance of visible ray.
In step (2), prepare respectively protective layer and resilient coating on the two sides of glass substrate.
Resilient coating comprises alternately laminated parylene film and inorganic matter film.
Protective layer comprises alternately laminated parylene film and inorganic matter film.
Parylene (Parylene) film is that then polymerization film formation is prepared from by hot ring crack solution.First solid-state ring disome is sublimed into gaseous state ring disome at 170 ° below C, then be cracked into stable unimolecule at 690 ± 10 ° of C gaseous state ring disomes, finally substrate is put into vacuum deposition chamber, make unimolecule enter vacuum moulding machine indoor, be adsorbed in glass substrate, and aggregate into linear polymeric polymer (Parylene).
Parylene is that C type ring disome polymerization (chloro-p-xylene) forms, and what therefore form is C type Parylene (poly).
Organic thin film has good pliability; its impact resistance is far above glass material; therefore the two sides being oppositely arranged in glass substrate all arranges parylene film can have good protective effect to glass; make its in use easy fracture not; improve overall toughness; and Parylene filming performance is good, the stress that can disperse well glass surface to produce in the time of deflection.In addition, parylene film has the transmitance very high in visible region, is beneficial to the bright dipping of device.
Preferably, parylene film is prepared by the following method: get solid-state paraxylene ring disome, after under 170 ° of C, distillation is gaseous state, cracking under 680～700 ° of C again, obtain the gaseous monomer molecule of the paraxylene with free radical, substrate is placed in to vacuum deposition chamber, passes into this gaseous monomer molecule, this gaseous monomer molecule aggregation also forms parylene film.
Preferably, the thickness of parylene film is 1～10 μ m.
Inorganic matter film is prepared by magnetically controlled sputter method.Sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, sputtering rate 0.2～2nm/s.
The inorganic matter film of protective layer is arranged on parylene film, can play the effect of protection parylene film, makes it not by exterior material deface, thereby has ensured the protective value of parylene film to glass.
The inorganic matter film of resilient coating is arranged between parylene film and anode, because the thermal coefficient of expansion of the anode materials such as Parylene and tin indium oxide (ITO) differs far away, therefore between anode and parylene film, add one deck inorganic oxide as buffering, can improve adhesive force between the two.Meanwhile, this inorganic matter film can be protected parylene film, makes it not by exterior material deface, thereby has ensured the protective value of parylene film to glass.
Inorganic matter film in protective layer is silicon dioxide or aluminium oxide.
Preferably, the thickness of the inorganic matter film in protective layer is 1～10 μ m.
Inorganic matter film in resilient coating is silicon dioxide or aluminium oxide.
Preferably, the thickness of the inorganic matter film in resilient coating is 0.2～2 μ m.
Inorganic matter film in inorganic matter film and resilient coating in protective layer can be identical or different material.
Preferably, the inorganic matter film in inorganic matter film and the resilient coating in protective layer is silicon dioxide.
In step (3), on resilient coating, prepare successively anode, functional layer and negative electrode.
Anode is prepared by sputtering method, and sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, sputtering rate 0.2～2nm/s.
Preferably, the material of anode is tin indium oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO) or gallium oxide zinc (GZO).
Preferably, the thickness of anode is 70～100nm.
Preferably, functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer are prepared by thermal resistance evaporation coating method.Evaporation condition comprises pressure 1 × 10
-5～1 × 10
-3pa, evaporation speed is 0.01～2nm/s.
Preferably, the material of hole injection layer is CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc) or phthalocyanine platinum (PtPc).
Preferably, the thickness of hole injection layer is 20～40nm.
Preferably, the material of hole transmission layer is 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) or 4,4', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).
Preferably, the thickness of hole transmission layer is 20～40nm.
Preferably, the material of luminescent layer is the material of main part doped with guest materials, described guest materials is 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 that iridium (FIrpic), two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid close iridium (FIr6), (acetylacetone,2,4-pentanedione) closes iridium (Ir (MDQ)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) or three (2-phenylpyridines) close iridium (Ir (ppy)
3), described material of main part is 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq
3), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), the doping mass fraction of described guest materials in material of main part is 1%～10%.
Also preferably, the material of luminescent layer is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4, two [4-(di-p-tolyl amino) styryl] biphenyl (DPAVBi) or 5 of 4'-, 6,11,12-tetraphenyl naphthonaphthalene (Rubrene).
Preferably, the thickness of luminescent layer is 1～20nm.
Preferably, the material of electron transfer layer is 2-(4-xenyl)-5-(4-the 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) or 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of electron transfer layer is 20～40nm.
Preferably, the material of electron injecting layer is lithium fluoride (LiF) or cesium fluoride (CsF).
Preferably, the thickness of electron injecting layer is 0.5～1nm.
Preferably, the material of negative electrode is argent (Ag), aluminium (Al), magnesium silver alloy (Mg-Ag) or magnadure (Mg-Al).
Preferably, the thickness of negative electrode is 70～200nm.
In step (4), encapsulated layer is arranged on to cathode surface.
Encapsulated layer and glass substrate are connected to form enclosure space, and anode, functional layer and negative electrode are placed in this enclosure space, for the infiltration of block water oxygen.
Preferably, encapsulated layer is alternately laminated silicon dioxide and silicon nitride.
More preferably, encapsulated layer is silicon dioxide and the silicon nitride of alternately laminated 3 times.
Preferably, the thickness of encapsulated layer is 600nm.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) organic electroluminescence device that the present invention makes is frivolous;
(2) OLED provided by the invention, prepare protective layer respectively on the two sides of substrate of glass and resilient coating has protective effect to glass, make it not by exterior material deface, improve overall toughness, and the stress that can disperse well glass surface to produce in the time of deflection, between anode and parylene film, add one deck inorganic oxide as buffering, can improve adhesive force between the two;
(3) encapsulated layer of the device infiltration of block water oxygen preferably, and keep higher transmitance, make device can obtain higher light extraction efficiency; In addition, parylene film has the transmitance very high in visible region, is also beneficial to the bright dipping of device.
(4) device has longer useful life, and preparation technology is simple, material source is extensive, and cost is low.
Brief description of the drawings
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in execution mode be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of the organic electroluminescence device prepared of the embodiment of the present invention 1;
Fig. 2 is protective layer, glass substrate and the resilient coating structural representation of the embodiment of the present invention 1 fabricate devices;
Fig. 3 is the functional layer structure schematic diagram of the organic electroluminescence device prepared of the embodiment of the present invention 1;
Fig. 4 is the number of bends-brightness contrast figure of the embodiment of the present invention 1～4 and comparative example fabricate devices.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment 1
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide thickness be the ultra-thin glass of 50 μ m as glass substrate, glass substrate comprises the first surface and the second surface that are oppositely arranged;
(2) prepare respectively protective layer and resilient coating at first surface and second surface:
A. get solid-state paraxylene ring disome, under 170 ° of C, distillation is for after gaseous state, then cracking under 690 ° of C, obtains the gaseous monomer molecule of the paraxylene with free radical;
B. glass substrate is placed in to vacuum deposition chamber, passes into gaseous monomer molecule, gaseous monomer molecule also forms respectively parylene film in first surface and the second surface polymerization of glass substrate;
C. be 5 × 10 in vacuum degree
-4in the sputter coating chamber of Pa, on the parylene film on first surface and second surface, silica membrane is prepared in sputter respectively, and sputtering condition is accelerating voltage 500V, magnetic field 100G, sputtering rate 1nm/s; Obtain being arranged on the protective layer on first surface and be arranged on the resilient coating on second surface;
(3) on resilient coating, prepare successively anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain the luminescence unit of preparation on resilient coating;
Particularly, the material of anode is ITO, and thickness is 100nm; The material of hole injection layer is CuPc, and thickness is 20nm; The material of hole transmission layer is NPB, and thickness is 30nm; The material of luminescent layer is Ir (ppy)
3be entrained in CBP Ir (ppy)
3doping mass fraction be 10%, thickness is 10nm; The material of electron transfer layer is Bphen, and thickness is 30nm; The material of electron injecting layer is LiF, and thickness is 1nm; The material of negative electrode is Ag, and thickness is 25nm, and structure is specifically expressed as ITO (100nm)/CuPc (20nm)/NPB (30nm)/Ir (ppy)
3: CBP (10%, 10nm)/Bphen (30nm)/LiF (1nm)/Ag (25nm); Wherein, slash "/" represents layer structure, Ir (ppy)
3: the colon ": " in CBP represents to mix, lower same;
Wherein, the sputtering condition of ITO is accelerating voltage 500V, magnetic field 100G, sputtering rate 1nm/s; Be 5 × 10 in vacuum degree
-4vacuum coating system in, the evaporation speed of CuPc and LiF is 0.1nm/s, NPB, Ir (ppy)
3being entrained in the mixture that forms in CBP and the evaporation speed of Bphen is 0.01nm/s, and the evaporation speed of Ag is 0.2nm/s;
(4) prepare encapsulated layer in the outside of luminescence unit, first sputter silicon dioxide, then sputtered silicon nitride, repeat 3 times altogether, and the encapsulated layer making is following stepped construction: silicon dioxide/silicon nitride/silicon dioxide/silicon nitride/silicon dioxide/silicon nitride.
Fig. 1 is the structural representation of the organic electroluminescence device prepared of the present embodiment 1, and organic electroluminescence device prepared by the present embodiment comprises protective layer 10, glass substrate 20, resilient coating 30, anode 40, functional layer 50, negative electrode 60, and encapsulated layer 70.
Fig. 2 is protective layer 10, glass substrate 20 and resilient coating 30 structural representations of the embodiment of the present invention 1 organic electroluminescence device; protective layer 10 comprises parylene film 101, inorganic matter film 102; resilient coating 30 comprises parylene film 301, inorganic matter film 302, and parylene film 101 and parylene film 301 are set directly at the two sides of glass substrate 20.
Fig. 3 is functional layer 50 structural representations of the embodiment of the present invention 1 organic electroluminescence device, and functional layer comprises the hole injection layer 501, hole transmission layer 502, luminescent layer 503, electron transfer layer 504 and the electron injecting layer 505 that stack gradually.
Embodiment 2
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide thickness be the ultra-thin glass of 50 μ m as glass substrate, glass substrate comprises the first surface and the second surface that are oppositely arranged;
(2) prepare respectively protective layer and resilient coating at first surface and second surface:
A. get solid-state paraxylene ring disome, under 170 ° of C, distillation is for after gaseous state, then cracking under 690 ° of C, obtains the gaseous monomer molecule of the paraxylene with free radical;
B. glass substrate is placed in to vacuum deposition chamber, passes into gaseous monomer molecule, gaseous monomer molecule also forms respectively parylene film in first surface and the second surface polymerization of glass substrate;
C. be 1 × 10 in vacuum degree
-5in the sputter coating chamber of Pa, on the parylene film on first surface and second surface, silica membrane is prepared in sputter respectively, and sputtering condition is accelerating voltage 300V, magnetic field 50G, sputtering rate 0.2nm/s; Obtain being arranged on the protective layer on first surface and be arranged on the resilient coating on second surface;
(3) on resilient coating, prepare successively anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain the luminescence unit of preparation on resilient coating;
Particularly, the material of anode is IZO, and thickness is 70nm; The material of hole injection layer is ZnPc, and thickness is 40nm; The material of hole transmission layer is 2-TNATA, and thickness is 40nm; The material of luminescent layer is Ir (piq)
3be entrained in NPB Ir (piq)
3mass fraction be 8%, thickness is 20nm; The material of electron transfer layer is TPBi, and thickness is 40nm; The material of electron injecting layer is CsF, and thickness is 1nm; The material of negative electrode is Al, and thickness is 200nm, and structure is specifically expressed as IZO (70nm)/ZnPc (40nm)/2-TNATA (40nm)/Ir (piq)
3: NPB (8%, 20nm)/TPBi (40nm)/CsF (1nm)/Al (200nm);
Wherein, the sputtering condition of IZO is accelerating voltage 300V, magnetic field 50G, sputtering rate 0.2nm/s; Be 1 × 10 in vacuum degree
-5vacuum coating system in, the evaporation speed of ZnPc and CsF is 0.5nm/s, 2-TNATA, Ir (piq)
3being entrained in the mixture that forms in NPB and the evaporation speed of TPBi is 0.5nm/s, and the evaporation speed of Al is 1nm/s;
(4) prepare encapsulated layer in the outside of luminescence unit, first sputter silicon dioxide, then sputtered silicon nitride, repeat 3 times altogether, and the encapsulated layer making is following stepped construction: silicon dioxide/silicon nitride/silicon dioxide/silicon nitride/silicon dioxide/silicon nitride.
Embodiment 3
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide thickness be the ultra-thin glass of 200 μ m as glass substrate, glass substrate comprises the first surface and the second surface that are oppositely arranged;
(2) prepare respectively protective layer and resilient coating at first surface and second surface:
A. get solid-state paraxylene ring disome, under 170 ° of C, distillation is for after gaseous state, then cracking under 690 ° of C, obtains the gaseous monomer molecule of the paraxylene with free radical;
B. glass substrate is placed in to vacuum deposition chamber, passes into gaseous monomer molecule, gaseous monomer molecule also forms respectively parylene film in first surface and the second surface polymerization of glass substrate;
C. be 1 × 10 in vacuum degree
-3in the sputter coating chamber of Pa, on the parylene film on first surface and second surface, aluminum oxide film is prepared in sputter respectively, and sputtering condition is accelerating voltage 800V, magnetic field 200G, sputtering rate 2nm/s; Obtain being arranged on the protective layer on first surface and be arranged on the resilient coating on second surface;
(3) on resilient coating, prepare successively anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain the luminescence unit of preparation on resilient coating;
Particularly, the material of anode is AZO, and thickness is 100nm; The material of hole injection layer is TiOPc, and thickness is 20nm; The material of hole transmission layer is m-MTDATA, and thickness is 20nm; The material of luminescent layer is that DCJTB is entrained in Alq
3in, the doping mass fraction of DCJTB is 1%, thickness is 1nm; The material of electron transfer layer is PBD, and thickness is 20nm; The material of electron injecting layer is CsF, and thickness is 0.5nm; The material of the first negative electrode is Mg-Ag, and thickness is 70nm, and structure is specifically expressed as AZO (100nm)/TiOPc (20nm)/m-MTDATA (20nm)/DCJTB:Alq
3(1%, 1nm)/PBD (20nm)/CsF (0.5nm)/Mg-Ag (70nm);
Wherein, the sputtering condition of AZO is accelerating voltage 800V, magnetic field 200G, sputtering rate 2nm/s; Be 1 × 10 in vacuum degree
-3vacuum coating system in, the evaporation speed of TiOPc and CsF is 1nm/s, m-MTDATA, DCJTB are entrained in Alq
3the evaporation speed of the mixture of middle formation and PBD is 1nm/s, and the evaporation speed of Mg-Ag is 2nm/s;
(4) prepare encapsulated layer in the outside of luminescence unit, first sputter silicon dioxide, then sputtered silicon nitride, repeat 3 times altogether, and the encapsulated layer making is following stepped construction: silicon dioxide/silicon nitride/silicon dioxide/silicon nitride/silicon dioxide/silicon nitride.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide thickness be the ultra-thin glass of 100 μ m as glass substrate, glass substrate comprises the first surface and the second surface that are oppositely arranged;
(2) prepare respectively protective layer and resilient coating at first surface and second surface:
A. get solid-state paraxylene ring disome, under 170 ° of C, distillation is for after gaseous state, then cracking under 690 ° of C, obtains the gaseous monomer molecule of the paraxylene with free radical;
B. glass substrate is placed in to vacuum deposition chamber, passes into gaseous monomer molecule, gaseous monomer molecule also forms respectively parylene film in first surface and the second surface polymerization of glass substrate;
C. be 1 × 10 in vacuum degree
-4in the sputter coating chamber of Pa, on the parylene film on first surface and second surface, aluminum oxide film is prepared in sputter respectively, and sputtering condition is accelerating voltage 600V, magnetic field 150G, sputtering rate 1.5nm/s; Obtain being arranged on the protective layer on first surface and be arranged on the resilient coating on second surface;
(3) on resilient coating, prepare successively anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain the luminescence unit of preparation on resilient coating;
Particularly, the material of anode is GZO, and thickness is 80nm; The material of hole injection layer is VOPc, and thickness is 20nm; The material of hole transmission layer is TPD, and thickness is 40nm; The material of luminescent layer is Rubrene, and thickness is 10nm; The material of electron transfer layer is BCP, and thickness is 40nm; The material of electron injecting layer is LiF, and thickness is 1nm; The material of negative electrode is Mg-Al, thickness is 100nm, and structure is specifically expressed as GZO (80nm)/VOPc (20nm)/TPD (40nm)/Rubrene (10nm)/BCP (40nm) LiF (1nm)/Mg-Al (100nm);
Wherein, the sputtering condition of GZO is accelerating voltage 600V, magnetic field 150G, sputtering rate 1.5nm/s; Be 1 × 10 in vacuum degree
-4vacuum coating system in, the evaporation speed of VOPc and LiF is 0.1nm/s, the evaporation speed of TPD, Rubrene and BCP is 0.01nm/s, the evaporation speed of Mg-Al is 0.2nm/s;
(4) prepare encapsulated layer in the outside of luminescence unit, first sputter silicon dioxide, then sputtered silicon nitride, repeat 3 times altogether, and the encapsulated layer making is following stepped construction: silicon dioxide/silicon nitride/silicon dioxide/silicon nitride/silicon dioxide/silicon nitride.
Comparative example
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) providing thickness is that the ultra-thin glass of 50 μ m is as glass substrate;
(3) in glass substrate, prepare successively anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain luminescence unit;
Particularly, the material of anode is ITO, and thickness is 100nm; The material of hole injection layer is CuPc, and thickness is 20nm; The material of hole transmission layer is NPB, and thickness is 30nm; The material of luminescent layer is Ir (ppy)
3be entrained in CBP Ir (ppy)
3doping mass fraction be 10%, thickness is 10nm; The material of electron transfer layer is Bphen, and thickness is 30nm; The material of electron injecting layer is LiF, and thickness is 1nm; The material of negative electrode is Ag, and thickness is 25nm, and structure is specifically expressed as ITO (100nm)/CuPc (20nm)/NPB (30nm)/Ir (ppy)
3: CBP (10%, 10nm)/Bphen (30nm)/LiF (1nm)/Ag (25nm);
Wherein, the sputtering condition of ITO is accelerating voltage 500V, magnetic field 100G, sputtering rate 1nm/s; Be 5 × 10 in vacuum degree
-4vacuum coating system in, the evaporation speed of CuPc and LiF is 0.1nm/s, NPB, Ir (ppy)
3being entrained in the mixture that forms in CBP and the evaporation speed of Bphen is 0.01nm/s, and the evaporation speed of Ag is 0.2nm/s;
(4) prepare encapsulated layer in the outside of luminescence unit, first sputter silicon dioxide, then sputtered silicon nitride, repeat 3 times altogether, and the encapsulated layer making is following stepped construction: silicon dioxide/silicon nitride/silicon dioxide/silicon nitride/silicon dioxide/silicon nitride.
Finally obtain organic electroluminescence device.
Fig. 4 be embodiment 1～4 under differently curved number of times, test be 1000cd/m in initial brightness
2time, brightness is with the variation of number of bends.Comparative example using with the ultra-thin glass of embodiment 1 condition of equivalent thickness as backing material, do not prepare resilient coating and protective layer, directly prepare OLED light-emitting device at glass baseplate surface.As can be seen from Figure 4, be 1000cd/m in initial brightness
2shi Jinhang deflection operation, the present invention invents the OLED providing after the bending of 200 times, and its brightness still can keep 700cd/m
2above, the brightness of comparative example device declines rapidly.Illustrate in deflection process do not having under the protection of resilient coating and protective layer, ultra-thin glass can destroy, and produces slight crack, and device performance is declined, until lost efficacy.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, anode, functional layer and negative electrode are cascading in glass substrate, at described cathode surface, encapsulated layer is set, make to form enclosure space between glass substrate and encapsulated layer, described anode, functional layer and negative electrode are contained in described enclosure space, it is characterized in that, between described glass substrate and anode, be provided with resilient coating, be provided with protective layer at the another side of described glass substrate;
Described resilient coating comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described resilient coating is silicon dioxide or aluminium oxide; Described protective layer comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described protective layer is silicon dioxide or aluminium oxide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, in described resilient coating, the thickness of parylene film is 1～10 μ m, and the thickness of inorganic matter film is 0.2～2 μ m.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, in described protective layer, the thickness of parylene film is 1～10 μ m, and the thickness of inorganic matter film is 1～10 μ m.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described encapsulated layer comprises alternately laminated silicon dioxide and silicon nitride.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
(1) provide glass substrate;
(2) prepare respectively protective layer and resilient coating on the two sides of described glass substrate, described resilient coating comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described resilient coating is silicon dioxide or aluminium oxide; Described protective layer comprises alternately laminated parylene film and inorganic matter film, and the inorganic matter film in described protective layer is silicon dioxide or aluminium oxide:
By paraxylene ring disome thermal cracking, then polymerization forms parylene film in described glass substrate; On described parylene film, inorganic matter film is prepared in sputter, and described inorganic matter film is silicon dioxide, silicon nitride or aluminium oxide, and sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, power density 1～40W/cm
2, sputtering rate 0.2～2nm/s;
(3) on described resilient coating, prepare successively anode, functional layer and negative electrode;
Wherein, described anode is prepared by sputtering method, and functional layer and negative electrode are prepared by thermal resistance evaporation coating method; Described sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, sputtering rate 0.2～2nm/s; Described thermal resistance evaporation condition is pressure 1 × 10
-5～1 × 10
-3pa, evaporation speed is 0.01～2nm/s;
(4) encapsulated layer is arranged on to described cathode surface, makes to form enclosure space between glass substrate and encapsulated layer, described anode, functional layer and negative electrode are contained in described enclosure space, and sputtering condition is vacuum degree 1 × 10
-5～1 × 10
-3pa, accelerating voltage 300～800V, magnetic field 50～200G, sputtering rate 0.2～2nm/s;
Finally obtain described organic electroluminescence device.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, in described resilient coating, the thickness of parylene film is 1～10 μ m, and the thickness of inorganic matter film is 0.2～2 μ m.
8. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, in described protective layer, the thickness of parylene film is 1～10 μ m, and the thickness of inorganic matter film is 1～10 μ m.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described encapsulated layer comprises alternately laminated silicon dioxide and silicon nitride.
10. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
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