CN100555707C - Adopt the organic electronic receptive layers to promote the Organic Light Emitting Diode that the hole is effectively injected - Google Patents
Adopt the organic electronic receptive layers to promote the Organic Light Emitting Diode that the hole is effectively injected Download PDFInfo
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- CN100555707C CN100555707C CNB2006100894457A CN200610089445A CN100555707C CN 100555707 C CN100555707 C CN 100555707C CN B2006100894457 A CNB2006100894457 A CN B2006100894457A CN 200610089445 A CN200610089445 A CN 200610089445A CN 100555707 C CN100555707 C CN 100555707C
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Abstract
A kind of organic electronic receptive layers that adopts promotes the Organic Light Emitting Diode that the hole is effectively injected, by forming with the lower part: a substrate; One positive pole is deposited on the substrate; One organic electronic receptive layers is deposited on the positive pole, is used for effectively transmitting electronics to positive pole; One thin metal layer is deposited on the organic electronic receptive layers, is used to produce electronics and hole; One organic hole implanted layer is deposited on the thin metal layer, is used for accepting the hole that thin metal layer produces; One organic cavity transmission layer is deposited on the organic hole implanted layer, is used for transporting holes; One organic light emission is deposited upon on the organic cavity transmission layer, is used to send visible light; One organic electron transport layer is deposited on the organic luminous layer, is used for transmission electronic; One cathodic deposition is on organic electron transport layer.
Description
Technical field
The present invention relates to contain the Organic Light Emitting Diode of organic electronic receptive layers, for example can visible emitting.The present invention relates to the preparation of Organic Light Emitting Diode, for example Organic Light Emitting Diode that contains a positive pole, an organic electronic receptive layers, a thin metal layer, an organic hole implanted layer, an organic cavity transmission layer, an organic luminous layer, an organic electron transport layer, a negative electrode of preparation on a substrate.
Background technology
Since Kodak in 1987 reported that double-deck Organic Light Emitting Diode, the beginning of the nineties, univ cambridge uk reported polymer LED, the research and the correlation technique of organic/polymer LED had obtained tremendous development.Up to the present, organic/polymer flat panel display is the coming into the market stage, and the organic solid lighting technology has also possessed market-oriented condition.The organic semiconducting materials flexibility is good, in light weight, processing simple, stable performance and can combining with the silica-based technology of tradition, the Organic Light Emitting Diode color is bright, the visual angle is wide, operating temperature range is big, low in energy consumption, can be used for moving and show product, have the low potentiality of production cost that therefore organic/polymer flat panel display is considered to substitute the optimal candidate of liquid crystal display; The energy is the necessary top-priority strategic issues in 21 century various countries, and reducing energy resource consumption is an important channel alleviating the energy shortage problem.Organic Light Emitting Diode all is better than present widely used incandescent lamp on life-span and efficient, so the organic solid lighting technology also is subjected to extensive concern.
The course of work of Organic Light Emitting Diode is made up of charge carrier injection, carrier transport, the compound attenuation then of charge carrier.Realize that it is the first step that realizes the high-performance Organic Light Emitting Diode that effective charge carrier injects.Charge carrier injects and to be meant that the hole injects and electronics injects from negative pole from positive pole.The positive pole of tin indium oxide (ITO) conductive film through being commonly used for Organic Light Emitting Diode realized the hole injection, and the metal of some high work contents for example gold, silver, platinum etc. also is used as the anodal hole injection that realizes.Often the organic hole injection material that uses mostly is CuPc, TPD, NPB, and their highest occupied molecular orbital (HOMO) energy level can be realized ohmic contact with above-mentioned positive pole between 5.0-5.7eV.Interfacial property between positive pole/hole injection layer directly determines the performance of device.Up to the present, do not see as yet about using the organic electronic acceptor material to participate in the report of the device of realization efficient hole injection.Often the organic electronic acceptor material that uses is C60, perylene tetracarboxylic acid dianhydride (PTCDA), 1,4,5,8-naphthalenetetracarbacidic acidic diimide (NTCDI), 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone (F4-TCNQ) etc., they can form exciton decomposition interface with the organic electronic donor material in organic solar batteries, realize effective separation in electronics one hole.Their minimum not occupied orbital (LUMO) energy level is relatively near the Fermi level of the contour work function metal of gold, silver.
Summary of the invention
The objective of the invention is to, provide a kind of organic electronic receptive layers that adopts to promote the Organic Light Emitting Diode that the hole is effectively injected, it can be applicable to organic flat panel display and solid state lighting device, has high and low driving voltage of brightness and the low advantage of cost.
A kind of organic electronic receptive layers that adopts of the present invention promotes the Organic Light Emitting Diode that the hole is effectively injected, it is characterized in that, by forming with the lower part:
One substrate;
One positive pole, this positive pole is deposited on the substrate;
One organic electronic receptive layers, this organic electronic receptive layers is deposited on the positive pole, is used for effectively transmitting electronics to positive pole;
One thin metal layer, this thin metal layer is deposited on the organic electronic receptive layers, is used to produce electronics and hole;
One organic hole implanted layer, this organic hole implanted layer is deposited on the thin metal layer, is used for accepting the hole that thin metal layer produces;
One organic cavity transmission layer, this organic cavity transmission layer is deposited on the organic hole implanted layer, is used for transporting holes;
One organic luminous layer, this organic light emission is deposited upon on the organic cavity transmission layer, is used to send visible light;
One organic electron transport layer, this organic electron transport layer is deposited on the organic luminous layer, is used for transmission electronic;
One negative electrode, this cathodic deposition is on organic electron transport layer.
Wherein the organic electronic receptive layers can be following arbitrary material:
C60, bisbenzimidazole generation-3,4,9,10-tetracarboxylic acid Ji perylene, perylene tetracarboxylic acid dianhydride.
Wherein thin metal layer can be following arbitrary material:
Tin indium oxide, silver, gold.
Wherein the organic hole implanted layer can be following arbitrary material:
Phthalocyanine Zinc, CuPc.
Wherein organic cavity transmission layer can be following arbitrary material:
N, N '-diphenyl-N, N '-two-1,1 '-diphenyl-4,4 '-diamines, N, N '-two-(3-aminomethyl phenyl)-N, N '-diphenyl-1,1 '-xenyl-4,4 '-diamines, 4,4 '-two-[N, N '-(3-tolyl) amino]-3,3 ' dimethyl diphenyl.
Wherein organic luminous layer is an oxine aluminium.
Wherein organic luminous layer oxine aluminium is with following arbitrary material doped:
N, N '-dimethylquinacridone, 3-(2 '-benzothiazolyl)-7-diethyl amino coumarin, rubrene, 4-(dicyano methylene)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans.
Wherein organic electron transport layer can be following arbitrary material:
Two (2-methyl-oxine)-4-biphenylyloxy aluminium, oxine aluminium.
Description of drawings
Fig. 1 promotes the structural representation of the Organic Light Emitting Diode that the hole is effectively injected for adopting the organic electronic receptive layers.
Fig. 2 is device ITO/PTCDA10nm/Ag5nm/CuPc5nm/NPB30nm/Alq
3The photoelectric properties of 60nm/Mg:Ag.
Fig. 3 is device ITO/PTCDA10nm/Ag5nm/CuPc5nm/NPB30nm/Alq
3The hole injection process of 60nm/Mg:Ag.
Embodiment
To will specifically describe the present invention with example, but the present invention is not limited only to cited example.
See also shown in Figure 1ly, the present invention is a kind of to adopt the organic electronic receptive layers to promote the Organic Light Emitting Diode that the hole is effectively injected, by forming with the lower part:
One substrate 90;
One positive pole 10, this positive pole 10 is deposited on the substrate 90;
One organic electronic receptive layers 20, this organic electronic receptive layers 20 are deposited on anodal 10, are used for effectively transmitting electronics to anodal 10; This organic electronic receptive layers 20 can be following arbitrary material: C60, PTCBI, PTCDA;
One thin metal layer 30, this thin metal layer 30 is deposited on the organic electronic receptive layers 20, is used to produce electronics and hole; This thin metal layer 30 can be following arbitrary material: ITO, Ag, Au;
One organic hole implanted layer 40, this organic hole implanted layer 40 is deposited on the thin metal layer 30, is used for accepting the hole that thin metal layer 30 produces; This organic hole implanted layer 40 can be following arbitrary material: ZnPc, CuPc;
One organic cavity transmission layer 50, this organic cavity transmission layer 50 is deposited on the organic hole implanted layer 40, is used for transporting holes; This organic cavity transmission layer 50 can be following arbitrary material: NPB, TPD, HMTPD;
One organic luminous layer 60, this organic luminous layer 60 is deposited on the organic cavity transmission layer 50, is used to send visible light; This organic luminous layer 60 is Alq
3
One organic electron transport layer 70, this organic electron transport layer 70 is deposited on the organic luminous layer 60, is used for transmission electronic; This organic luminous layer 70 can be with following arbitrary material doped: DMQA, Coumarin 6, Rubrene, DCM;
One negative electrode 80, this cathodic deposition is on organic electron transport layer 70; This organic electron transport layer 80 can be following arbitrary material: BAlq
2, Alq
3
Involved in the present invention is that a kind of organic electronic acceptor that adopts promotes the Organic Light Emitting Diode that the hole is effectively injected.That is to say, contain one deck at Organic Light Emitting Diode involved in the present invention and directly contact anodal organic electronic receptor film.For example, such one is adopted Organic Light Emitting Diode that the organic electronic acceptor realizes injecting in the hole to form 80 by a positive pole 10, organic electronic receptive layers 20, thin metal layer 30, organic hole implanted layer 40, organic cavity transmission layer 50, organic luminous layer 60, organic electron transport layer 70, a negative electrode.
In the present invention, anodal 10 are generally ito glass, also can be translucent metal electrode, for example gold, silver, platinum.
In the present invention, organic electronic receptive layers 20 should have stronger electron transport ability, and the relatively more approaching work content of using positive electrode usually of lumo energy, and energy level difference should not be higher than 0.5eV.In the present invention, can be C60, PTCBI, PTCDA as the material of organic electronic receptive layers 20.
In the present invention, thin metal layer 30 should play to the organic electronic receptive layers and inject electronics and to the effect of organic hole layer injected hole, must be semitransparent thin film.In the present invention, thin metal layer 30 should possess higher work content, can be ITO, gold, silver, platinum etc.
In the present invention, to such an extent as to the material of organic hole implanted layer 40 be meant those can be smoothly, the organic molecule material that can fine realization hole injects of the anodal surface of parent's profit.The HOMO energy level of the material of organic hole implanted layer 40 should be complementary with the thin metal layer work content, and the energy barrier difference is not higher than 0.7eV, can be ZnPc, CuPc.
In the present invention, the material of organic cavity transmission layer 50 is meant that those possess the organic molecule material of higher hole mobility, preferential conduction hole.Can be NPB, TPD, HMTPD.
In the present invention, the material of organic luminous layer 60 should send visible light, can have widely to select, and organic luminous layer can be sent out blue streak (J.Appl.Phys.84,2324 (1998)); (Appl.Phys.Lett.75,1682 (1999)) can glow; Can send out triplet state light (J.Appl.Phys.97,044505 (2005)); Also can be a kind of combination emit white light (Appl.Phys.Lett.86,113507 (2005)).
In the present invention, the material of organic electron transport layer 70 is meant that those possess the organic molecule material of high electron mobility, preferential conduction electron.The lumo energy of organic electron transport layer 70 materials should be complementary with the negative electrode work content, and the energy barrier difference is not higher than 0.7eV, can be Alq
3
In the present invention, negative electrode 80 can be magnesium/silver combination or magnesium silver alloy or lithium fluoride/aluminium combination.
Characteristics of the present invention and advantage:
(1) the present invention has changed the design philosophy of traditional Organic Light Emitting Diode, adopts the organic receptor material of stable performance to promote the hole to inject, and has tangible independent intellectual property right.
(2) because the level structure of organic receptor material and the work content of normally used positive electrode are mated more, and it is very good that effect is injected in the hole, can be issued to high brightness in low-voltage, illumination is very useful for organic semiconductor for this.
Example 1:
The employing organic electronic receptive layers that the present invention relates to promotes the Organic Light Emitting Diode that the hole is effectively injected, and its device architecture is ITO/PTCDA 10nm/Ag5nm/CuPc5nm/NPB30nm/Alq
360nm/Mg:Ag.Fig. 2 has provided the photoelectric properties of this device.As can be seen, though be mingled with the PTCDA film of one deck 10 nanometers between ITO and 5 Nano Silver films, it is very good that situation is injected in the hole of this device, can send very strong green-yellow light.This is that the first in the world only adopts the organic receptor material to realize the Organic Light Emitting Diode that the hole is injected.Fig. 3 has provided the operation principle of this device.Under certain bias voltage, the silver-colored film of 5 nanometers is polarized, thereby has generated the hole and the electronics of some; Under effect of electric field, the hole is injected in the CuPc film, and electronics is injected into and advances ITO in the PTCDA film then.So just finished the hole injection process.
Claims (8)
1, a kind of organic electronic receptive layers that adopts promotes the Organic Light Emitting Diode that the hole is effectively injected, it is characterized in that, by forming with the lower part:
One substrate;
One positive pole, this positive pole is deposited on the substrate;
One organic electronic receptive layers, this organic electronic receptive layers is deposited on the positive pole, is used for effectively transmitting electronics to positive pole;
One thin metal layer, this thin metal layer is deposited on the organic electronic receptive layers, is used to produce electronics and hole;
One organic hole implanted layer, this organic hole implanted layer is deposited on the thin metal layer, is used for accepting the hole that thin metal layer produces;
One organic cavity transmission layer, this organic cavity transmission layer is deposited on the organic hole implanted layer, is used for transporting holes;
One organic luminous layer, this organic light emission is deposited upon on the organic cavity transmission layer, is used to send visible light;
One organic electron transport layer, this organic electron transport layer is deposited on the organic luminous layer, is used for transmission electronic;
One negative electrode, this cathodic deposition is on organic electron transport layer.
2, employing organic electronic receptive layers according to claim 1 promotes the Organic Light Emitting Diode that the hole is effectively injected, and it is characterized in that wherein the organic electronic receptive layers can be following arbitrary material:
C60, bisbenzimidazole generation-3,4,9,10-tetracarboxylic acid Ji perylene, perylene tetracarboxylic acid dianhydride.
3, employing organic electronic receptive layers according to claim 1 promotes the Organic Light Emitting Diode that the hole is effectively injected, and it is characterized in that wherein thin metal layer can be following arbitrary material:
Tin indium oxide, silver, gold.
4, employing organic electronic receptive layers according to claim 1 promotes the Organic Light Emitting Diode that the hole is effectively injected, and it is characterized in that wherein the organic hole implanted layer can be following arbitrary material:
Phthalocyanine Zinc, CuPc.
5, employing organic electronic receptive layers according to claim 1 promotes the Organic Light Emitting Diode that the hole is effectively injected, and it is characterized in that wherein organic cavity transmission layer can be following arbitrary material:
N, N '-diphenyl-N, N '-two-1,1 '-diphenyl-4,4 '-diamines, N, N '-two-(3-aminomethyl phenyl)-N, N '-diphenyl-1,1 '-xenyl-4,4 '-diamines, 4,4 '-two-[N, N '-(3-tolyl) amino]-3,3 ' dimethyl diphenyl.
6, employing organic electronic receptive layers according to claim 1 promotes the Organic Light Emitting Diode that the hole is effectively injected, and it is characterized in that wherein organic luminous layer is an oxine aluminium.
7, employing organic electronic receptive layers according to claim 6 promotes the Organic Light Emitting Diode that the hole is effectively injected, and it is characterized in that wherein organic luminous layer oxine aluminium is with following arbitrary material doped:
N, N '-dimethylquinacridone, 3-(2 '-benzothiazolyl)-7-diethyl amino coumarin, rubrene, 4-(dicyano methylene)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans.
8, employing organic electronic receptive layers according to claim 1 promotes the Organic Light Emitting Diode that the hole is effectively injected, and it is characterized in that wherein organic electron transport layer can be following arbitrary material:
Two (2-methyl-oxine)-4-biphenylyloxy aluminium, oxine aluminium.
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| WO2009125471A1 (en) * | 2008-04-07 | 2009-10-15 | パイオニア株式会社 | Light emitting element and display panel |
| WO2009125472A1 (en) * | 2008-04-07 | 2009-10-15 | パイオニア株式会社 | Light emitting element and display panel |
| WO2017156433A1 (en) * | 2016-03-10 | 2017-09-14 | Red Bank Technologies Llc. | Bank edge emission enhanced organic light emitting diode utilizing chiral liquid crystalline emitter |
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| CN1610469A (en) * | 2003-02-03 | 2005-04-27 | 三星Sdi株式会社 | Organic electroluminescent device driven at low voltage |
| US20050106419A1 (en) * | 2003-11-13 | 2005-05-19 | International Manufacturing And Engineering Services Co., Ltd. | Organic electroluminescent devices |
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| CN1610469A (en) * | 2003-02-03 | 2005-04-27 | 三星Sdi株式会社 | Organic electroluminescent device driven at low voltage |
| US20050106419A1 (en) * | 2003-11-13 | 2005-05-19 | International Manufacturing And Engineering Services Co., Ltd. | Organic electroluminescent devices |
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