CN104051634A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104051634A CN104051634A CN201310076778.6A CN201310076778A CN104051634A CN 104051634 A CN104051634 A CN 104051634A CN 201310076778 A CN201310076778 A CN 201310076778A CN 104051634 A CN104051634 A CN 104051634A
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/311—Phthalocyanine
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- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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- H—ELECTRICITY
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- 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
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Abstract
The invention relates to an organic light-emitting device which includes a transmitting substrate and an anode layer, an inorganic oxide layer, an organic layer, an organic light-emitting function layer and a cathode layer, which are arranged on the transmitting substrate sequentially in a laminated manner. The material of the inorganic oxide layer is MoO3, ReO3, WO3, Sb2O3 or NiO. The material of the organic layer is a metal phthalocyanine complex. Compared with a traditional light-emitting device, the organic light-emitting device is higher in light-emitting efficiency under a condition that the driving voltages are identical, that is, the organic light-emitting device is capable of working under a lower driving voltage so that the organic light-emitting device is higher in service life. The invention also provides a preparation method for the organic light-emitting device.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, particularly relate to a kind of Organnic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode, OLED) device has that brightness is high, material range of choice is wide, driving voltage is low, entirely solidifies the characteristics such as active illuminating, have the advantages such as high definition, wide viewing angle and fast response time simultaneously, 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.
Although the scientific research personnel of various countries, the whole world is by selecting suitable organic material and rational luminous device structure to design, made the indices of light-emitting device performance be greatly improved, but traditional light-emitting device needs larger driving voltage and luminous efficiency low, but also has low problem of light-emitting device life-span.In order to realize the practical of Organnic electroluminescent device, it is little that people are eager to find a kind of driving voltage, the Organnic electroluminescent device that luminous efficiency is high.
The luminous efficiency of Organnic electroluminescent device depends on injection efficiency, the efficiency of transmission of charge carrier conventionally, and and the efficiency of exciton recombination luminescence.Wherein, charge carrier comprises hole and electronics, and raising Carrier Injection Efficiency can make to collide in device and the hole-duplet of radioluminescence increases, thereby can greatly improve luminous efficiency.Hole is relevant with the injection barrier between anode and organic luminescence function layer in injection efficiency, and electronics is relevant with the injection barrier of negative electrode and organic luminescence function layer in injection efficiency.But the HOMO energy level of organic luminescence function layer is conventionally at 5.1～5.7eV, and the work content on common anode surface is more much lower than it, and if the work content on conventional ito anode surface is 4.7eV, so the potential barrier that hole is injected into organic luminescence function layer from anode is higher.Thereby the injection efficiency in hole is lower, and then cause the luminous efficiency of Organnic electroluminescent device lower, and need larger driving voltage.
Summary of the invention
Based on this, be necessary the Organnic electroluminescent device that provides a kind of luminous efficiency higher.
An Organnic electroluminescent device, comprises light-transparent substrate and is cascadingly set on anode layer, inorganic oxide layer, organic layer, organic luminescence function layer and the cathode layer in described light-transparent substrate; The material of described inorganic oxide layer is molybdenum trioxide (MoO
3), rhenium trioxide (ReO
3), tungstic acid (WO
3), antimonous oxide (Sb
2o
3) or nickel oxide (NiO); The material of described organic layer is metal phthalocyanine complex.
In an embodiment, described metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc or phthalocyanine platinum therein.
In an embodiment, the thickness of described inorganic oxide layer is 1～10nm therein; The thickness of described organic layer is 5～20nm.
In an embodiment, described organic luminescence function layer comprises hole transmission layer, luminescent layer and the electron transfer layer being cascading therein, and wherein, described hole transmission layer is located on described anode layer.
In an embodiment, the material of described hole transmission layer is 4,4 ＇ therein, 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; The material of described electron transfer layer is 2-(4-xenyl)-5-(the 4-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, described luminescent layer is the mixture of luminescent material and material of main part, described luminescent 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, three (1-phenyl-isoquinolin) 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 luminescent material and described material of main part is 1%～10%, or
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.
In an embodiment, the thickness of described hole transmission layer is 20～60nm therein, and the thickness of described luminescent layer is 1～20nm, and the thickness of described electron transfer layer is 20～60nm.
In an embodiment, the material of described anode layer is indium tin oxide, indium-zinc oxide, aluminium zinc oxide or gallium zinc oxide therein, and the thickness of described anode layer is 70～200nm.
Therein in an embodiment, described cathode layer comprises lithium fluoride (LiF) layer and is arranged on metal level or the metal alloy layer on described LiF layer, described metal level is silver layer or aluminium lamination, described metal alloy layer is magnadure or magnesium silver alloy, the thickness of described LiF layer is 1nm, and the thickness of described metal level or metal alloy layer is 70～200nm.
A preparation method for Organnic electroluminescent device, comprises the steps:
In vacuum coating system, on light-transparent substrate surface, anode layer is prepared in sputter;
In vacuum coating system, on described anode layer, adopt thermal evaporation techniques or electron beam evaporation technique to prepare inorganic oxide layer, obtain intermediate product, and described intermediate product is placed in to vacuum environment at 200～600 ℃, carries out annealing in process, wherein, the material of described inorganic oxide layer is MoO
3, ReO
3, WO
3, Sb
2o
3or NiO;
In vacuum coating system, on described inorganic oxide layer, adopt thermal evaporation techniques to stack gradually and prepare organic layer, organic luminescence function layer and cathode layer, wherein, the material of described organic layer is metal phthalocyanine complex.
Above-mentioned Organnic electroluminescent device by setting up an inorganic oxide layer on anode layer, and this inorganic oxide layer has higher surperficial work content, mates with the energy level with the organic luminescence function layer of higher energy level.Make the hole producing on anode layer from anode layer, be injected into the potential barrier reduction of organic luminescence function layer, thereby the injection efficiency in hole increases, make to collide the also hole-duplet of radioluminescence and increase in organic luminescence function layer, and then greatly improve the luminous efficiency of Organnic electroluminescent device.Above-mentioned Organnic electroluminescent device is compared with traditional light-emitting device, under the identical condition of driving voltage, have higher luminous efficiency, above-mentioned Organnic electroluminescent device can be worked under lower driving voltage, thereby makes it have higher useful life.The preparation method of above-mentioned Organnic electroluminescent device, carries out heating anneal processing to the intermediate product that contains inorganic oxide layer, can improve the crystalline state on inorganic oxide layer surface, thus the better effects if that hole is injected.Adopting thermal evaporation techniques to prepare organic layer, organic luminescence function layer and cathode layer, is mainly for fear of damaging organic layer and organic luminescence function layer.In addition, above-mentioned preparation method's technique is simple, process is easy to control, and suitable industrialization is produced.
Accompanying drawing explanation
Fig. 1 is the structural representation of the Organnic electroluminescent device of an execution mode;
Fig. 2 is the voltage-to-current density characteristic curve figure of the Organnic electroluminescent device of embodiment 1 and comparative example made.
Embodiment
Below in conjunction with drawings and the specific embodiments, Organnic electroluminescent device and preparation method thereof is further detailed.
As shown in Figure 1, the Organnic electroluminescent device 100 of an execution mode, comprises light-transparent substrate 110, anode layer 120, inorganic oxide layer 130, organic layer 140, organic luminescence function layer 150 and cathode layer 160.
Anode layer 120 is arranged in light-transparent substrate 110, and inorganic oxide layer 130 is arranged at anode layer 120, and organic layer 140 is arranged at inorganic oxide layer 130, and organic luminescence function layer 150 is arranged at organic layer 140, and cathode layer 160 is arranged at organic luminescence function layer 150.
In the present embodiment, light-transparent substrate 110 is clear glass.Be appreciated that in other embodiments, light-transparent substrate 100 can be also other materials.
The material of anode layer 120 is transparent conductive oxide film, can be indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO).The thickness of anode layer 120 is 70～200nm.Be appreciated that in other embodiments, anode layer 120 can also be other transparent conductive oxide films, and its thickness is also not limited to 70～200nm, meets and has good conductive capability and make Organnic electroluminescent device have suitable size.
The material of inorganic oxide layer 130 is MoO
3, ReO
3, WO
3, Sb
2o
3or NiO.MoO
3, ReO
3, WO
3, Sb
2o
3and NiO has the higher higher surperficial work content that has, mate with the energy level with the organic luminescence function layer of higher energy level.The thickness of inorganic oxide layer 130 is 1～10nm.
The material of organic layer 140 is metal phthalocyanine complex, can be CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc) or phthalocyanine platinum (PtPc).Metal phthalocyanine complex has good energy level with organic luminescence function layer and mates, and has again good film forming, while contacting with inorganic oxide layer, can form band curvature, hole is injected and be more prone to.The thickness of organic layer 140 is 5～20nm.
Organic luminescence function layer 150 comprises hole transmission layer 152, luminescent layer 154 and the electron transfer layer 156 being cascading.
In the present embodiment, hole transmission layer 152 is by 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) triphenylamine (TCTA) prepares.
Luminescent layer 154 is obtained by luminescent material and material of main part mixture.Wherein, luminescent 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 (FI6), 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 (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 mass percent 1%～10% of luminescent material and material of main part.
Luminescent layer 154 also can adopt phosphor material to prepare.As prepared by 4,4 ＇-bis-(2,2-diphenylethyllene)-1,1 ＇-biphenyl (DPVBi), 4,4 ＇-bis-[4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) or 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene).
Electron transfer layer 156 is by 2-(4-xenyl)-5-(the 4-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) prepares.
In the present embodiment, the thickness of hole transmission layer 152 is 20～60nm, and the thickness of luminescent layer 154 is 1～20nm, and the thickness of electron transfer layer 156 is 20～60nm.
Cathode layer 160 comprises LiF layer 162 and is arranged on metal level or the metal alloy layer 164 on LiF layer 162.Metal level or metal alloy layer 164 can be silver layer, aluminium lamination, magnadure layer or magnesium ag alloy layer.The thickness of LiF layer 164 is 1nm, and the thickness of metal or metal alloy layer 164 is 70～200nm.
Above-mentioned Organnic electroluminescent device by setting up an inorganic oxide layer on anode layer, and this inorganic oxide layer has higher surperficial work content, mates with the energy level with the organic luminescence function layer of higher energy level.Make the hole producing on anode layer from anode layer, be injected into the potential barrier reduction of organic luminescence function layer, thereby the injection efficiency in hole increases, make to collide the also hole-duplet of radioluminescence and increase in organic luminescence function layer, and then greatly improve the luminous efficiency of Organnic electroluminescent device.Above-mentioned Organnic electroluminescent device is compared with traditional light-emitting device, under the identical condition of driving voltage, have higher luminous efficiency, above-mentioned Organnic electroluminescent device can be worked under lower driving voltage, thereby makes it have higher useful life.
But inorganic oxide layer is normally directly prepared through high temperature, and its surface crystallization is perfect not, has many defects, the raising effect that it is injected hole is stable not.If inorganic oxide layer ingress of air or standing time are longer, its surface is some impurity of absorption and steam easily, and surperficial work content is declined rapidly.Therefore, above-mentioned Organnic electroluminescent device also arranges an organic layer to address the above problem on inorganic oxide layer.The material of this organic layer is phthalocyanine metal complex, has good energy level mate with organic luminescence function layer, has again good film forming, while contacting with inorganic oxide layer, can form band curvature, hole is injected and be more prone to.In addition, for mate the inorganic oxide layer that is not very desirable with organic luminescence function layer energy level, can also play a supplementary effect, thereby make the selection of inorganic oxide more extensive, can select the inorganic oxide of relative low price.
In addition, in present embodiment, also provide a kind of preparation method of Organnic electroluminescent device, comprise the steps:
Step S110, provides light-transparent substrate.
Light-transparent substrate is clear glass.Light-transparent substrate need to be through prior processing, concrete processing procedure is: light-transparent substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dry up with nitrogen, standby.
Step S120, in vacuum coating system, on light-transparent substrate surface, above-mentioned anode layer is prepared in sputter.
The material selection transparent conductive oxide of anode layer can be indium tin oxide, indium-zinc oxide, aluminium zinc oxide or gallium zinc oxide.The thickness of anode layer 120 is 70～200nm.
Step S130, in vacuum coating system, on anode layer, adopt thermal evaporation techniques or electron beam evaporation technique to prepare above-mentioned inorganic oxide layer, obtain intermediate product, and intermediate product is placed in to vacuum environment at 200～600 ℃, carries out annealing in process 0.1～1 hour.
Vacuum degree in vacuum coating system is 5 * 10
-4pa.
Vacuum degree in vacuum environment is 1 * 10
-3pa～1 * 10
-5pa.
The material of inorganic oxide layer is MoO
3, ReO
3, WO
3, Sb
2o
3or NiO.MoO
3, ReO
3, WO
3, Sb
2o
3and NiO has the higher higher surperficial work content that has, mate with the energy level with the organic luminescence function layer of higher energy level.The thickness of inorganic oxide layer is 1～10nm.
Step S140 in vacuum coating system, adopts thermal evaporation techniques to stack gradually preparation above-mentioned organic layer, organic luminescence function layer and cathode layer on inorganic oxide layer.
The material of organic layer is metal phthalocyanine complex, can be CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc) or phthalocyanine platinum (PtPc).Metal phthalocyanine complex has good energy level with organic luminescence function layer and mates, and has again good film forming, while contacting with inorganic oxide layer, can form band curvature, hole is injected and be more prone to.The thickness of organic layer 140 is 5～20nm.
Organic luminescence function layer comprises hole transmission layer, luminescent layer and the electron transfer layer being cascading.
In the present embodiment, hole transmission layer is by 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) triphenylamine (TCTA) prepares.
Luminescent layer is obtained by luminescent material and material of main part mixture.Wherein, luminescent 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 (FI6), 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 (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 mass percent of luminescent material and material of main part is 1%～10%.
Luminescent layer also can adopt phosphor material to prepare.As prepared by 4,4 ＇-bis-(2,2-diphenylethyllene)-1,1 ＇-biphenyl (DPVBi), 4,4 ＇-bis-[4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) or 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene).
Electron transfer layer is by 2-(4-xenyl)-5-(the 4-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) prepares.
In the present embodiment, the thickness of the hole transmission layer preparing is 20～60nm, and the thickness of luminescent layer is 1～20nm, and the thickness of electron transfer layer is 20～60nm.
Cathode layer comprises LiF layer and is arranged on metal level or the metal alloy layer on LiF layer.Metal level or metal alloy layer can be silver layer, aluminium lamination, magnadure layer or magnesium ag alloy layer.The thickness of LiF layer is 1nm, and the thickness of metal or metal alloy layer is 70～200nm.
The preparation method of above-mentioned Organnic electroluminescent device, carries out heating anneal processing to the intermediate product that contains inorganic oxide layer, can improve the crystalline state on inorganic oxide layer surface, thus the better effects if that hole is injected.Adopting thermal evaporation techniques to prepare organic layer, organic luminescence function layer and cathode layer, is mainly for fear of damaging organic layer and organic luminescence function layer.In addition, above-mentioned preparation method's technique is simple, process is easy to control, and suitable industrialization is produced.
Be below specific embodiment and comparative example part, wherein, "/" represents stacked, and ": " represents that the former (luminescent material) is entrained in formation composite material in the latter's (material of main part), parenthetic percentage data representation luminescent material and the mass percent of material of main part.
Embodiment 1
Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned clear glass, sputter prepares the ito anode layer that thickness is 100nm.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned ito anode layer surface, adopt thermal evaporation techniques to prepare the MoO that thickness is 3nm
3inorganic oxide layer.To contain MoO
3it is 1 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-4in the vacuum environment of Pa, and at 500 ℃, carry out annealing in process 0.5 hour.
By the MoO that contains after heating anneal is processed
3it is 5 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-4in the vacuum coating system of Pa, in MoO
3on inorganic oxide layer, adopt thermal evaporation techniques to stack gradually to prepare the Ag layer that LiF layer that ZnPc organic layer, organic luminescence function layer, thickness that thickness is 10nm are 1nm and thickness are 100nm.
Wherein, organic luminescence function layer comprises the NPB hole transmission layer that the thickness that stacks gradually is 30nm, DCJTB and the Alq that thickness is 1nm
3hybrid illuminating layer (DCJTB and Alq
3mass percent be 1%) and the thickness Bphen electron transfer layer that is 30nm.
The representation of above-mentioned Organnic electroluminescent device is: clear glass/ITO (100nm)/MoO
3(3nm)/ZnPc (10nm)/NPB (30nm)/DCJTB:Alq
3(1%, 1nm)/Bphen (30nm)/LiF (1nm)/Ag (100nm)
Embodiment 2
Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned clear glass, sputter prepares the ito anode layer that thickness is 100nm.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned ito anode layer surface, adopt thermal evaporation techniques to prepare the ReO that thickness is 1nm
3inorganic oxide layer.To contain ReO
3it is 1 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-3in the vacuum environment of Pa, and at 200 ℃, carry out annealing in process 0.1 hour.
By the ReO that contains after heating anneal is processed
3it is 5 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-4in the vacuum coating system of Pa, in ReO
3on inorganic oxide layer, adopt thermal evaporation techniques to stack gradually to prepare the Al layer that LiF layer that CuPc organic layer, organic luminescence function layer, thickness that thickness is 5nm are 1nm and thickness are 70nm.
Wherein, organic luminescence function layer comprises the 2-TNATA hole transmission layer that the thickness that stacks gradually is 60nm, the Ir (piq) that thickness is 12nm
3hybrid illuminating layer (Ir (piq) with CBP
3with the mass percent of CBP be 8%) and the thickness TPBi electron transfer layer that is 60nm.
The representation of above-mentioned Organnic electroluminescent device is: clear glass/ITO (100nm)/ReO
3(1nm)/CuPc (5nm)/2-TNATA (60nm)/Ir (piq)
3: CBP (8%, 12nm)/TPBi (60nm)/LiF (1nm)/Al (70nm)
Embodiment 3
Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned clear glass, sputter prepares the GZO anode layer that thickness is 200nm.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned GZO anode layer surface, adopt thermal evaporation techniques to prepare the WO that thickness is 10nm
3inorganic oxide layer.To contain WO
3it is 1 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-5in the vacuum environment of Pa, and at 600 ℃, carry out annealing in process 1 hour.
By the WO that contains after heating anneal is processed
3it is 5 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-4in the vacuum coating system of Pa, in WO
3on inorganic oxide layer, adopt thermal evaporation techniques to stack gradually to prepare the magnadure layer that LiF layer that TiOPc organic layer, organic luminescence function layer, thickness that thickness is 20nm are 1nm and thickness are 200nm.
Wherein, organic luminescence function layer comprises the m-MTDATA hole transmission layer that the thickness that stacks gradually is 20nm, the Ir (ppy) that thickness is 15nm
3hybrid illuminating layer (Ir (piq) with CBP
3with the mass percent of CBP be 10%) and the thickness PBD electron transfer layer that is 20nm.
The representation of above-mentioned Organnic electroluminescent device is: clear glass/GZO (200nm)/WO
3(10nm)/TiOPc (20nm)/m-MTDATA (20nm)/Ir (ppy)
3: CBP (10%, 15nm) PBD (20nm)/LiF (1nm)/Al-Mg (200nm)
Embodiment 4
Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned clear glass, sputter prepares the IZO anode layer that thickness is 100nm.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned IZO anode layer surface, adopt thermal evaporation techniques to prepare the Sb that thickness is 5nm
2o
3inorganic oxide layer.To contain Sb
2o
3it is 5 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-4in the vacuum environment of Pa, and at 400 ℃, carry out annealing in process 0.5 hour.
By the Sb that contains after heating anneal is processed
2o
3it is 5 * 10 that the intermediate product of inorganic oxide layer is placed in vacuum degree
-4in the vacuum coating system of Pa, in Sb
2o
3on inorganic oxide layer, adopt thermal evaporation techniques to stack gradually to prepare the magnesium ag alloy layer that LiF layer that VOPc organic layer, organic luminescence function layer, thickness that thickness is 15nm are 1nm and thickness are 120nm.
Wherein, organic luminescence function layer comprises the BCP electron transfer layer that TPD hole transmission layer that the thickness that stacks gradually is 40nm, DPVBi luminescent layer that thickness is 20nm and thickness are 40nm.
The representation of above-mentioned Organnic electroluminescent device is: clear glass/IZO (100nm)/Sb
2o
3(5nm)/VOPc (15nm)/TPD (40nm)/DPVBi (20nm)/BCP (40nm)/LiF (1nm)/Ag-Mg (120nm)
Embodiment 5
Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned clear glass, sputter prepares the IZO anode layer that thickness is 100nm.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned IZO anode layer surface, adopt thermal evaporation techniques to prepare the NiO inorganic oxide layer that thickness is 5nm.It is 1 * 10 that the intermediate product that contains NiO inorganic oxide layer is placed in to vacuum degree
-4in the vacuum environment of Pa, and at 600 ℃, carry out annealing in process 1 hour.
It is 5 * 10 that the intermediate product that contains NiO inorganic oxide layer after heating anneal is processed is placed in to vacuum degree
-4in the vacuum coating system of Pa, on NiO inorganic oxide layer, adopt thermal evaporation techniques to stack gradually to prepare the magnesium ag alloy layer that LiF layer that PtPc organic layer, organic luminescence function layer, thickness that thickness is 10nm are 1nm and thickness are 120nm.
Wherein, organic luminescence function layer comprises the TCTA hole transmission layer that the thickness that stacks gradually is 40nm, FIrpic and the hybrid illuminating layer (mass percent of FIrpic and CBP is 10%) of CBP and the TAZ electron transfer layer that thickness is 35nm that thickness is 15nm.
The representation of above-mentioned Organnic electroluminescent device is: and clear glass/IZO (100nm)/NiO (5nm)/PtPc (10nm)/TCTA (40nm)/FIrpic:CBP (10%, 15nm)/TAZ (35nm)/LiF (1nm)/Ag-Mg (120nm)
Comparative example
Clear glass is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen, standby.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned clear glass, sputter prepares the ito anode layer that thickness is 100nm.
In vacuum degree, be 5 * 10
-4in the vacuum coating system of Pa, on above-mentioned ito anode layer surface, adopt thermal evaporation techniques to prepare the silver layer that LiF layer that organic luminescence function layer, thickness are 1nm and thickness are 100nm.
Wherein, organic luminescence function layer comprises the NPB hole transmission layer that the thickness that stacks gradually is 30nm, DCJTB and the Alq that thickness is 1nm
3hybrid illuminating layer (DCJTB and Alq
3mass percent be 1%) and the thickness Bphen electron transfer layer that is 30nm.
The representation of above-mentioned Organnic electroluminescent device is: clear glass/ITO (100nm)/NPB (30nm)/DCJTB:Alq
3(1%, 1nm)/Bphen (30nm)/LiF (1nm)/Ag (100nm)
Performance Detection
Table 1 is the luminescent properties data of the Organnic electroluminescent device of embodiment 1-5 made and the light-emitting device of comparative example made.As can be seen from the table, the Organnic electroluminescent device that embodiment 1-5 makes is compared with common light-emitting device (not containing inorganic oxide layer and organic layer), owing to having adopted inorganic oxide layer and organic layer, the injection efficiency in hole is improved, thereby can obviously see that the starting resistor of the Organnic electroluminescent device needs of embodiment 1-5 made is starkly lower than comparative example.The efficiency that hole is injected has improved, thereby the luminous efficiency of Organnic electroluminescent device has also improved.And the starting resistor that Organnic electroluminescent device needs reduced, also can relatively increase the useful life of Organnic electroluminescent device.
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example |
| Starting resistor | 2.5 | 2.6 | 2.7 | 2.8 | 2.8 | 3.1 |
| Luminous efficiency (1m/W) | 11.6 | 16.7 | 21.5 | 10.1 | 11.5 | 7.6 |
Fig. 2 is under identical experiment condition, the voltage-to-current density characteristic curve figure of the Organnic electroluminescent device of embodiment 1 and comparative example made.Fig. 2 shows under identical driving voltage condition, because the Organnic electroluminescent device of embodiment 1 made contains inorganic oxide layer and organic layer, the injection efficiency in hole is improved, the injection number in hole is many, therefore under identical voltage conditions, the Organnic electroluminescent device of embodiment 1 made 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 Organnic electroluminescent device, is characterized in that, comprises light-transparent substrate and is cascadingly set on anode layer, inorganic oxide layer, organic layer, organic luminescence function layer and the cathode layer in described light-transparent substrate; The material of described inorganic oxide layer is molybdenum trioxide, rhenium trioxide, tungstic acid, antimonous oxide or nickel oxide; The material of described organic layer is metal phthalocyanine complex.
2. Organnic electroluminescent device as claimed in claim 1, is characterized in that, described metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, ranadylic phthalocyanine, TiOPc or phthalocyanine platinum.
3. Organnic electroluminescent device as claimed in claim 1, is characterized in that, the thickness of described inorganic oxide layer is 1～10nm; The thickness of described organic layer is 5～20nm.
4. Organnic electroluminescent device as claimed in claim 1, is characterized in that, described organic luminescence function layer comprises hole transmission layer, luminescent layer and the electron transfer layer being cascading, and wherein, described hole transmission layer is located on described anode layer.
5. Organnic electroluminescent 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; The material of described electron transfer layer is 2-(4-xenyl)-5-(the 4-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.
6. Organnic electroluminescent device as claimed in claim 4, it is characterized in that, described luminescent layer is the mixture of luminescent material and material of main part, described luminescent 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, three (1-phenyl-isoquinolin) 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 luminescent material and described material of main part is 1%～10%, or
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.
7. the Organnic electroluminescent device as described in any one in claim 4-6, is characterized in that, the thickness of described hole transmission layer is 20～60nm, and the thickness of described luminescent layer is 1～20nm, and the thickness of described electron transfer layer is 20～60nm.
8. Organnic electroluminescent device as claimed in claim 1, is characterized in that, the material of described anode layer is indium tin oxide, indium-zinc oxide, aluminium zinc oxide or gallium zinc oxide, and the thickness of described anode layer is 70～200nm.
9. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, described cathode layer comprises lithium fluoride layer and is arranged on metal level or the metal alloy layer on described lithium fluoride layer, described metal level is silver layer or aluminium lamination, described metal alloy layer is magnadure layer or magnesium ag alloy layer, the thickness of described lithium fluoride layer is 1nm, and the thickness of described metal level or metal alloy layer is 70～200nm.
10. a preparation method for Organnic electroluminescent device, is characterized in that, comprises the steps:
In vacuum coating system, on light-transparent substrate surface, anode layer is prepared in sputter;
In vacuum coating system, on described anode layer, adopt thermal evaporation techniques or electron beam evaporation technique to prepare inorganic oxide layer, obtain intermediate product, and described intermediate product is placed in to vacuum environment at 200～600 ℃, carries out annealing in process, wherein, the material of described inorganic oxide layer is molybdenum trioxide, rhenium trioxide, tungstic acid, antimonous oxide or nickel oxide;
In vacuum coating system, on described inorganic oxide layer, adopt thermal evaporation techniques to stack gradually and prepare organic layer, organic luminescence function layer and cathode layer, wherein, the material of described organic layer is metal phthalocyanine complex.
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