CN104051632A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104051632A CN104051632A CN201310076758.9A CN201310076758A CN104051632A CN 104051632 A CN104051632 A CN 104051632A CN 201310076758 A CN201310076758 A CN 201310076758A CN 104051632 A CN104051632 A CN 104051632A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/816—Multilayers, e.g. transparent multilayers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
Abstract
The invention relates to an organic light-emitting device. The device includes a base, an anode layer, a hole injection modification layer, an organic light-emitting function layer and a cathode layer, which are designed to be laminated sequentially. The material of the hole injection modification layer is a mixed material formed through mixing of a metal oxide and a metal phthalocyanine complex according to a quality ratio of 1:0.1-1, wherein the metal oxide is MoO3, ReO3, WO3, Sb2O3 or NiO and the metal phthalocyanine complex is copper phthalocyanine, zinc phthalocyanine, vanadyl phthalocyanine, oxotitanium phthalocyanine or platinum phthalocyanine. The organic light-emitting is provided with the hole injection modification layer which is formed through mixing of an organic material and an inorganic material so that the potential barrier between the anode layer and the organic light-emitting function layer is reduced and the organic material is better in film forming property and thus preparation of a smoother hole injection layer film is facilitated so that it is convenient for holes to be injected from the anode layer from the organic light-emitting function layer; and when the hole injection modification layer contacts the organic light-emitting function layer, energy band bending can also be formed so that hole injection is easier.
Description
Technical field
The present invention relates to electroluminescence field, especially relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission 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.
Up to the present, although the scientific research personnel of various countries, the whole world is by selecting suitable organic material and rational device structure design, made the indices of device performance be greatly improved, but at present owing to driving the electric current of luminescent device large, the problem such as luminous efficiency is low and device lifetime is low, in order to realize the practical of organic electroluminescence device, it is little that people are eager to find a kind of drive current, the luminescent device structure that luminous efficiency is high.The hole injection efficiency of organic electroluminescence device is relevant with the injection barrier between anode and organic layer, conventionally the work content on anode ITO surface is 4.7eV, and the HOMO energy level of organic layer is conventionally at 5.1-5.7eV, therefore the potential barrier that hole is injected into organic layer from anode is higher, the drive current that whole device needs is larger, has limited it and has further applied.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of drive current is less and preparation method thereof.
A kind of organic electroluminescence device, comprise the substrate, anode layer, hole injection decorative layer, organic luminescence function layer and the cathode layer that stack gradually design, wherein, the material that decorative layer is injected in described hole is the composite material that ratio that metal oxide and metal phthalocyanine complex are 1:0.1～1 according to mass ratio is mixed to form, and described metal oxide is molybdenum trioxide (MoO
3), rhenium trioxide (ReO
3), tungstic acid (WO
3), antimonous oxide (Sb
2o
3) or nickel oxide (NiO), described metal phthalocyanine complex is CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc) or phthalocyanine platinum (PtPc).
In an embodiment, described anode layer is transparent conductive oxide film therein.
In an embodiment, described transparent conductive oxide film is indium and tin oxide film, indium-zinc oxide film, aluminium zinc oxide film or gallium zinc oxide film therein.
Therein in an embodiment, described organic luminescence function layer comprises that being located at described hole injects hole transmission layer on decorative layer, is located at the luminescent layer on described hole transmission layer and is located at the electron transfer layer on described luminescent layer.
Therein in an embodiment, the material of described hole transmission layer is 4,4 ', 4 " tri-(2-naphthyl phenyl amino) triphenylamine, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1; 1 '-biphenyl-4,4 '-diamines, 4,4 '; 4 "-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines or 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines.
Therein in an embodiment, the material of described electron transfer layer is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-diazole, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 1,2,4-triazole derivative.
Therein in an embodiment, the material of described luminescent layer is that phosphor material is entrained in the composite material forming in material of main part, wherein, described phosphor material is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium and three (1-phenyl-isoquinolin) and close iridium and three (2-phenylpyridine) and close at least one in iridium, described material of main part is 4, 4 '-bis-(9-carbazole) biphenyl, oxine aluminium, 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene or N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines, the mass percent of described phosphor material and described material of main part is 1～10%.
In an embodiment, the material of described luminescent layer is 4,4 '-bis-(2,2-diphenylethyllene)-1,1 '-biphenyl, 4,4 '-bis-[4-(di-p-tolyl is amino) styryl] biphenyl or 5,6,11,12-tetraphenyl naphthonaphthalene therein.
In an embodiment, described cathode layer comprises near lithium fluoride (LiF) layer of described anode layer and is located at metal level or the metal alloy layer on described LiF layer therein.
A preparation method for organic electroluminescence device, comprises the steps:
In vacuum coating system, in substrate surface sputter, prepare anode layer;
In vacuum coating system, pass through thermal evaporation techniques, evaporated metal oxide and metal phthalocyanine complex form hole injection decorative layer respectively, the evaporation rate of described metal oxide is 0.2nm/s～2nm/s, the ratio of the evaporation rate of described metal oxide and metal phthalocyanine complex is 1:0.1～1, and described metal oxide is MoO
3, ReO
3, WO
3, Sb
2o
3or NiO, described metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc or phthalocyanine platinum;
In vacuum coating system, in described hole, inject on decorative layer successively that evaporation is prepared organic light emitting functional layer and cathode layer obtains described organic electroluminescence device.
Above-mentioned organic electroluminescence device mixes the metal oxide with raising hole injectability with metal phthalocyanine complex, be prepared into the hole injection decorative layer that a kind of organic material and inorganic material mix, reduce the potential barrier between anode layer and organic luminescence function layer, and organic material has good film forming, be conducive to the more smooth hole injection layer film of preparation, thereby be conducive to hole and be injected into organic luminescence function layer from anode layer, when this hole injection decorative layer contacts with organic luminescence function layer, can also form band curvature, hole is injected to be more prone to.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is brightness-current density characteristic curve of the organic electroluminescence device of embodiment 1 and comparative example 1 making.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of an execution mode comprises substrate 110, anode layer 120, hole injection decorative layer 130, organic luminescence function layer 140 and the cathode layer 150 that stacks gradually design.
Substrate 110 is that transparent material makes, as clear glass etc.
Anode layer 120 is transparent conductive oxide film, as indium and tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO) etc.The thickness of anode layer 120 is between 70～200nm.
The material that decorative layer 130 is injected in hole is the composite material that ratio that metal oxide and metal phthalocyanine complex are 1:0.1～1 according to mass ratio is mixed to form.Wherein, metal oxide is MoO
3, ReO
3, WO
3, Sb
2o
3or NiO.Metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc or phthalocyanine platinum.
Organic luminescence function layer 140 comprises that being located at hole injects hole transmission layer 142 on decorative layer 130, is located at the luminescent layer 144 on hole transmission layer 142 and is located at the electron transfer layer 146 on luminescent layer 144.
The material of hole transmission layer 142 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).The thickness of hole transmission layer 142 is between 20～60nm.
The material of electron transfer layer 146 is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-diazole (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 1,2,4-triazole derivative (TAZ).The thickness of electron transfer layer 146 is between 20～60nm.
The material of luminescent layer 144 is that phosphor material is entrained in the composite material forming in material of main part, wherein, phosphor material 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 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) and three (2-phenylpyridines) close at least one in iridium (Ir (ppy) 3).Material of main part is 4,4 '-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq3), 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 mass percent of phosphor material and material of main part is 1～10%.Or the material of luminescent layer 144 is 4,4 '-bis-(2,2-diphenylethyllenes)-1,1 '-biphenyl (DPVBi), 4,4 '-bis-[4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) or 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene).The thickness of luminescent layer 144 is between 1～20nm.
Cathode layer 150 comprises near the LiF layer of anode layer 120 and is located at metal level or the metal alloy layer on LiF layer, as the alloy-layer of alloy-layer, Mg and the Al of Ag layer, Al layer, Mg and Ag etc.Wherein, the thickness of LiF layer is 1nm, and the thickness of metal level or metal alloy layer is between 70～200nm.
Above-mentioned organic electroluminescence device mixes the metal oxide with raising hole injectability with metal phthalocyanine complex, be prepared into the hole injection decorative layer that a kind of organic material and inorganic material mix, reduce the potential barrier between anode layer and organic luminescence function layer, and organic material has good film forming, be conducive to the more smooth hole injection layer film of preparation, thereby be conducive to hole and be injected into organic luminescence function layer from anode layer, when this hole injection decorative layer contacts with organic luminescence function layer, can also form band curvature, hole is injected to be more prone to.In addition, in the hole injection layer of this mixing, added the extraordinary inorganic material of thermal stability, hole injection layer can retention be stablized in long use procedure, even the variation of organic material generation partial properties, inorganic material still can guarantee hole injection effect.
In addition, present embodiment also provides a kind of preparation method of organic electroluminescence device, comprises the steps:
Step 1: in vacuum coating system, prepare anode layer in substrate surface sputter;
Substrate is that transparent material is made, as clear glass etc.Anode layer is transparent conductive oxide film, as indium and tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO) etc.The thickness of the anode layer of preparation is between 70～200nm.
Step 2: in vacuum coating system, pass through thermal evaporation techniques, evaporated metal oxide and metal phthalocyanine complex form hole injection decorative layer respectively, the evaporation rate of metal oxide is between 0.2nm/s～2nm/s, the ratio of the evaporation rate of metal oxide and metal phthalocyanine complex is between 1:0.1～1, and metal oxide is MoO
3, ReO
3, WO
3, Sb
2o
3or NiO, metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc or phthalocyanine platinum;
Step 3: in vacuum coating system, inject in hole on decorative layer that evaporation is prepared organic light emitting functional layer and cathode layer obtains organic electroluminescence device.
Organic luminescence function layer comprises that being located at hole injects hole transmission layer on decorative layer, is located at the luminescent layer on hole transmission layer and is located at the electron transfer layer on luminescent layer.
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).The thickness of hole transmission layer prepared by present embodiment is between 20～60nm.
The material of electron transfer layer is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-diazole (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 1,2,4-triazole derivative (TAZ).The thickness of electron transfer layer prepared by present embodiment is between 20～60nm.
The material of luminescent layer is that phosphor material is entrained in the composite material forming in material of main part, wherein, phosphor material 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 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) and three (2-phenylpyridines) close at least one in iridium (Ir (ppy) 3).Material of main part is 4,4 '-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq3), 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 mass percent of phosphor material and material of main part is 1～10%.Or the material of luminescent layer is 4,4 '-bis-(2,2-diphenylethyllenes)-1,1 '-biphenyl (DPVBi), 4,4 '-bis-[4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) or 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene).The thickness of the luminescent layer that present embodiment prepares is between 1～20nm.
Cathode layer comprises near the LiF layer of anode layer and is located at metal level or the metal alloy layer on LiF layer, as the alloy-layer of alloy-layer, Mg and the Al of Ag layer, Al layer, Mg and Ag etc.Wherein, the thickness of LiF layer is 1nm, and the thickness of metal level or metal alloy layer is between 70～200nm.
Above-mentioned preparation process principle is simple, low for equipment requirements, easy to utilize.
Be below specific embodiment and comparative example part, wherein, "/" represents stacked, and ": " represents that the former (for the material adulterating) is entrained in the composite material that the latter's (material of main part) forms, and parenthetic percentage data representation is the mass percent at material of main part for the material that adulterates.
Embodiment 1
The structure of organic electroluminescence device is: substrate of glass/ITO (100nm)/MoO
3: ZnPc (1:0.1,20nm)/NPB (30nm)/DCJTB:Alq
3(1%, 1nm)/Bphen (30nm)/LiF (1nm)/Ag (100nm).
The manufacture method of the organic electroluminescence device of the present embodiment, comprises following step:
Step 1, provide substrate of glass, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen.
Step 2, in vacuum coating system, in substrate surface sputter, preparing a layer thickness is that the ITO layer of 100nm is as anode layer.
Step 3, in vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, prepare hole inject decorative layer on anode layer surface by thermal evaporation, material is MoO
3with the mixture of ZnPc, MoO
3with the mass ratio of ZnPc be 1:0.1, wherein MoO
3evaporation rate be 0.5nm/s, the evaporation rate of znPc is 0.05nm/s.The thickness that decorative layer is injected in the hole of preparation is 20nm.
Step 4, treat said process after, on decorative layer is injected in hole, preparing structure is NPB (30nm)/DCJTB:Alq
3(1%, the organic luminescence function layer of 1nm)/Bphen (30nm), wherein, NPB is hole transmission layer, DCJTB:Alq
3for luminescent layer, Bphen is electron injecting layer.
Step 5, in vacuum coating system, utilize thermal evaporation techniques on organic luminescence function layer, to prepare the LiF layer that thickness is 1nm and on LiF layer, prepare the Ag layer that thickness is 100nm to form composite cathode layer, thereby obtain having the organic electroluminescence device of said structure.
Embodiment 2
The structure of organic electroluminescence device is: substrate of glass/ITO (100nm)/ReO
3: CuPc (1:0.5,40nm)/2-TNATA (60nm)/Ir (piq)
3: CBP (8%, 12nm)/TPBi (60nm)/LiF (1nm)/Al (70nm).
The manufacture method of the organic electroluminescence device of the present embodiment, comprises following step:
Step 1, provide substrate of glass, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen.
Step 2, in vacuum coating system, in substrate surface sputter, preparing a layer thickness is that the ITO layer of 100nm is as anode layer.
Step 3, in vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, prepare hole inject decorative layer on anode layer surface by thermal evaporation, material is ReO
3with the mixture of CuPc, ReO
3with the mass ratio of CuPc be wherein ReO of 1:0.5
3evaporation rate be 2nm/s, the evaporation rate of ZnPc is 1nm/s.The thickness that decorative layer is injected in hole is 40nm.
Step 4, treat said process after, on decorative layer is injected in hole, preparing structure is 2-TNATA (60nm)/Ir (piq)
3: CBP (8%, the organic luminescence function layer of 12nm)/TPBi (60nm), wherein, 2-TNATA is hole transmission layer, Ir (piq)
3: CBP is luminescent layer, and TPBi is electron transfer layer.
Step 5, in vacuum coating system, utilize thermal evaporation techniques on organic luminescence function layer, to prepare the LiF layer that thickness is 1nm and on LiF layer, prepare the Al layer that thickness is 70nm to form composite cathode layer, thereby obtain having the organic electroluminescence device of said structure.
Embodiment 3
The structure of organic electroluminescence device is: substrate of glass/GZO (200nm)/WO
3: TiOPc (1:1,5nm)/m-MTDATA (20nm)/Ir (ppy)
3: CBP (10%, 15nm)/PBD (20nm)/LiF (1nm)/Al-Mg (200nm).
The manufacture method of the organic electroluminescence device of the present embodiment, comprises following step:
Step 1, provide substrate of glass, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen.
Step 2, in vacuum coating system, in substrate surface sputter, preparing a layer thickness is that the GZO of 200nm is as anode layer.
Step 3, in vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, prepare hole inject decorative layer on anode layer surface by thermal evaporation, material is WO
3with the mixture of TiOPc, WO
3with the mass ratio of TiOPc be 1:1, wherein WO
3evaporation rate be 0.02nm/s, the evaporation rate of ZnPc is 0.02nm/s.The thickness that decorative layer is injected in hole is 5nm.
Step 4, treat said process after, on decorative layer is injected in hole, preparing structure is m-MTDATA (20nm)/Ir (ppy)
3: CBP (10%, the organic luminescence function layer of 15nm)/PBD (20nm), wherein, m-MTDATA is hole transmission layer, Ir (ppy)
3: CBP is luminescent layer, and PBD is electron transfer layer.
Step 5, utilize thermal evaporation techniques on organic luminescence function layer, to prepare the LiF layer that thickness is 1nm and on LiF layer, prepare magnadure (Mg-Al) that thickness is 200nm layer and form composite cathode layer, thereby obtain having the organic electroluminescence device of said structure.
Embodiment 4
The structure of organic electroluminescence device is: substrate of glass/IZO (100nm)/Sb
2o
3: VOPc (1:0.5,25nm)/TPD (40nm)/DPVBi (20nm)/BCP (40nm)/LiF (1nm)/Ag-Mg (120nm).
The manufacture method of the organic electroluminescence device of the present embodiment, comprises following step:
Step 1, provide substrate of glass, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen.
Step 2, in vacuum coating system, in substrate surface sputter, preparing a layer thickness is that the IZO of 100nm is as anode layer.
Step 3, in vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, prepare hole inject decorative layer on anode layer surface by thermal evaporation, material is Sb
2o
3with the mixture of VOPc, Sb
2o
3with the mass ratio of VOPc be wherein Sb of 1:0.5
2o
3evaporation rate be 0.8nm/s, the evaporation rate of ZnPc is 0.4nm/s.The thickness that decorative layer is injected in hole is 25nm.
Step 4, treat said process after, on decorative layer is injected in hole, prepare the organic luminescence function layer that structure is Ei TPD (40nm)/DPVBi (20nm)/BCP (40nm), wherein, TPD is hole transmission layer, DPVBi is luminescent layer, and BCP is electron transfer layer.
Step 5, utilize thermal evaporation techniques on organic luminescence function layer, to prepare the LiF layer that thickness is 1nm and on LiF layer, prepare silver-colored magnesium alloy (Ag-Mg) that thickness is 120nm layer and form composite cathode layer, thereby obtain having the organic electroluminescence device of said structure.
Embodiment 5
The structure of organic electroluminescence device is: substrate of glass/IZO (100nm)/NiO:PtPc (1:1,30nm)/TCTA (40nm)/FIrpic:CBP (10%, 15nm)/TAZ (35nm)/LiF (1nm)/Ag-Mg (120nm).
The manufacture method of the organic electroluminescence device of the present embodiment, comprises following step:
Step 1, provide substrate of glass, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen.
Step 2, in vacuum coating system, in substrate surface sputter, preparing a layer thickness is that the IZO of 100nm is as anode layer.
Step 3, in vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, prepare hole inject decorative layer at anode surface by thermal evaporation, material is the mixture of NiO and PtPc, and the mass ratio of NiO and PtPc is 1:1, and wherein the evaporation rate of NiO is 0.5nm/s, and the evaporation rate of PtPc is 0.5nm/s.The thickness that decorative layer is injected in hole is 30nm.
Step 4, treat said process after, on decorative layer is injected in hole, preparing structure is TCTA (40nm)/FIrpic:CBP (10%, the organic luminescence function layer of 15nm)/TAZ (35nm), wherein, TCTA is hole transmission layer, FIrpic:CBP is luminescent layer, and TAZ is electron transfer layer.
Step 5, utilize thermal evaporation techniques on organic luminescence function layer, to prepare the LiF layer that thickness is 1nm and on LiF layer, prepare silver-colored magnesium alloy (Ag-Mg) that thickness is 120nm layer and form composite cathode layer, thereby obtain having the organic electroluminescence device of said structure.
Comparative example 1
The structure of organic electroluminescence device is: substrate of glass/ITO (100nm)/NPB (30nm)/DCJTB:Alq
3(1%, 1nm)/Bphen (30nm)/LiF (1nm)/Ag (100nm).
The manufacture method of the organic electroluminescence device of this comparative example, comprises following step:
Step 1, provide substrate of glass, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, after cleaning up, with isopropyl alcohol, acetone, in ultrasonic wave, process 20 minutes successively, and then dry up with nitrogen.
Step 2, in vacuum coating system, in substrate surface sputter, preparing a layer thickness is that the ITO of 100nm is as anode layer.
Step 3, in vacuum degree, be 5 * 10
-4in the vacuum coating system of pa, the luminescent layer DCJTB:Alq that the NPB for preparing successively thickness on anode layer surface and be 30nm is 1nm as hole transmission layer, thickness
3(DCJTB and Alq
3mass percent be 1%) and thickness be 30nm electron transfer layer Bphen forms organic light emitting functional layer.
Step 4, utilize thermal evaporation techniques to prepare the LiF layer that thickness is 1nm and on LiF layer, prepare Ag layer that thickness is 100nm at organic luminescence function layer upper surface to form composite cathode layer, thereby obtain having the organic electroluminescence device of said structure.
Comparative example 1 is compared with embodiment, and it is not prepared hole at anode surface and injects decorative layer.
Table 1 is embodiment 1,2,3,4,5 and the luminescent properties data of the device of comparative example 1 made, as follows:
Table 1
| ? | Starting resistor | Luminous efficiency (lm/W) |
| Embodiment 1 | 2.5 | 12.1 |
| Embodiment 2 | 2.5 | 17.2 |
| Embodiment 3 | 2.6 | 22.1 |
| Embodiment 4 | 2.8 | 11.7 |
| Embodiment 5 | 2.7 | 12.9 |
| Comparative example 1 | 3.1 | 7.6 |
As can be seen from Table 1, the organic electroluminescence device that EXAMPLE l-5 make is compared with the device of comparative example 1, owing to having adopted hole to inject decorative layer, the injection efficiency in hole is improved, thereby can obviously reduce starting resistor.Because starting resistor reduces, hole is injected and is improved, thereby the luminous efficiency of its device has also improved.
Fig. 2 is the device of embodiment 1 made and the voltage-to-current density characteristic curve of the device that comparative example 1 is made.As can be seen from Figure, under the identical condition of driving voltage, because the hole injection efficiency of the organic electroluminescence device of embodiment 1 preparation is higher, the injection number in hole is many, therefore has higher Injection Current.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic electroluminescence device, it is characterized in that, comprise the substrate, anode layer, hole injection decorative layer, organic luminescence function layer and the cathode layer that stack gradually design, wherein, the material that decorative layer is injected in described hole is the composite material that ratio that metal oxide and metal phthalocyanine complex are 1:0.1～1 according to mass ratio is mixed to form, described metal oxide is molybdenum trioxide, rhenium trioxide, tungstic acid, antimonous oxide or nickel oxide, and described metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc or phthalocyanine platinum.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described anode layer is transparent conductive oxide film.
3. organic electroluminescence device as claimed in claim 2, is characterized in that, described transparent conductive oxide film is indium and tin oxide film, indium-zinc oxide film, aluminium zinc oxide film or gallium zinc oxide film.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, described organic luminescence function layer comprises that being located at described hole injects hole transmission layer on decorative layer, is located at the luminescent layer on described hole transmission layer and is located at the electron transfer layer on described luminescent layer.
5. organic electroluminescence device as claimed in claim 4, it is characterized in that, the material of described hole transmission layer is 4,4', 4''-tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines or 4,4', 4''-tri-(carbazole-9-yl) triphenylamine.
6. organic electroluminescence device as claimed in claim 4, is characterized in that, the material of described electron transfer layer is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-diazole, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 1,2,4-triazole derivative.
7. organic electroluminescence device as claimed in claim 4, it is characterized in that, the material of described luminescent layer is that phosphor material is entrained in the composite material forming in material of main part, wherein, described phosphor material is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium and three (1-phenyl-isoquinolin) and close iridium and three (2-phenylpyridine) and close at least one in iridium, described material of main part is 4, 4'-bis-(9-carbazole) biphenyl, oxine aluminium, 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, the mass percent of described phosphor material and described material of main part is 1～10%.
8. organic electroluminescence device as claimed in claim 4, is characterized in that, the material of described luminescent layer is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl, 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl or 5,6,11,12-tetraphenyl naphthonaphthalene.
9. organic electroluminescence device as claimed in claim 1, is characterized in that, described cathode layer comprises near the lithium fluoride layer of described anode layer and is located at metal level or the metal alloy layer on described lithium fluoride layer.
10. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
In vacuum coating system, in substrate surface sputter, prepare anode layer;
In vacuum coating system, pass through thermal evaporation techniques, evaporated metal oxide and metal phthalocyanine complex form hole injection decorative layer respectively, the evaporation rate of described metal oxide is 0.2nm/s～2nm/s, the ratio of the evaporation rate of described metal oxide and metal phthalocyanine complex is 1:0.1～1, described metal oxide is molybdenum trioxide, rhenium trioxide, tungstic acid, antimonous oxide or nickel oxide, and described metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc or phthalocyanine platinum;
In vacuum coating system, on described hole injection decorative layer, evaporation is prepared organic light emitting functional layer and cathode layer successively, obtains described organic electroluminescence device.
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