CN101800290A - Organic LED by adopting doped metallic oxide as hole injection structure - Google Patents
Organic LED by adopting doped metallic oxide as hole injection structure Download PDFInfo
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- CN101800290A CN101800290A CN200910077680A CN200910077680A CN101800290A CN 101800290 A CN101800290 A CN 101800290A CN 200910077680 A CN200910077680 A CN 200910077680A CN 200910077680 A CN200910077680 A CN 200910077680A CN 101800290 A CN101800290 A CN 101800290A
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Abstract
The invention discloses an organic LED by adopting doped metallic oxide as a hole injection structure, which comprises a transparent anode, an organic hole injection layer, an organic hole transmission layer, an organic luminescent layer, an organic electronic transmission layer and a cathode; wherein the organic hole injection layer is deposited on the transparent anode and the area of the organic hole injection layer is smaller than that of the transparent anode; the organic hole injection transmission layer is deposited on the organic hole injection layer; the organic luminescent layer is deposited on the organic hole injection transmission layer; the electronic transmission layer is deposited on the organic luminescent layer; the cathode is deposited on the organic electronic transmission layer and the area of the cathode is smaller than that of the organic electronic transmission layer.
Description
Technical field
The present invention relates to a kind of preparation of Organic Light Emitting Diode, being specifically related to Dinging Xing of the transition metal oxide doping Gao Wen perylene that a kind of employing has a high work function is the Organic Light Emitting Diode of derivant material as hole injection structure, can be applied to the emission of visible light and near infrared light.
Background technology
Organic electroluminescent LED (OLED) has that the material range of choice is wide, driving voltage is low, solidifies active illuminating entirely, in light weight, operating temperature range is wide and can be produced on the first-class characteristics of soft substrate, can satisfy the current Information technology epoch to the more requirement of high-performance and bigger information capacity of Display Technique, become one of popular topic of present scientific circles and industrial circle.In addition, because the high efficiency, low cost of OLED also is expected its application prospect at lighting field.
Thereby the performance that improves organic electroluminescence device strengthens the competitiveness of organic electroluminescent product in market, is crucial for the development of current organic electroluminescent technology.The performance of organic electroluminescence device is luminosity, the current efficiency depressed of same electrical for example, the injection efficiency of lumen luminous efficiency, starting resistor and device stability etc. and charge carrier and inject balance very big relation is arranged.The injection in hole and transmission are the key factors that restriction organic electroluminescent technical development and performance improve always.When negative electrode and anode can both well inject charge carrier, the mobility of charge carrier in organic material became the principal element that influences the device operating voltage.In addition, though current limited in the injection of charge carrier, the charge velocity of charge carrier still is directly proportional with the mobility of organic material.Therefore, exploitation has the effective way that organic transferring material of high carrier mobility also is the raising device performance.
The mode that adopts transition metal oxide to mix is effectively to improve the method for hole injectability.Dong-Seok Leem ReO
3Doping NPB is as hole injection layer, and a bright voltage of device is 5.2-5.4V, is 20mA/cm in current density
2Under energy efficiency be 2.2-2.3lm/W.Chan-Ching Chang uses WO
3Doping 2-TNATA, device play bright voltage 3.1V, maximum power efficiency 3.5lm/W.And the thermal stability of all these devices all improves a lot.The transition metal oxide that this class hole injection layer is adopted all has high work function, can reduce the potential barrier that the hole is injected.And these metal oxides have the stronger electronic capability that gets, and can improve the concentration in hole after the doping, help the injection in hole.But up to the present, not seeing about use transition metal oxide to mix having electronic transmission performance De perylene as yet is the report of derivant material as the device of hole injection layer.
Summary of the invention
The present invention proposes that a kind of to adopt transition metal oxide Can Za perylene be the Organic Light Emitting Diode of derivant material as hole injection structure, can be applicable to organic flat panel display and solid state lighting field.
The invention provides a kind of Organic Light Emitting Diode that adopts doped metallic oxide as hole injection structure, it is characterized in that, comprising:
One transparent anode;
One organic hole implanted layer, this organic hole implanted layer is deposited on the described transparent anode, and the area of this organic hole implanted layer is less than the area of transparent anode;
One organic cavity transmission layer, this organic cavity transmission layer are deposited on the described organic hole implanted layer;
One organic luminous layer, this organic light emission are deposited upon on the described organic cavity transmission layer;
One organic electron transport layer, this organic electron transport layer are deposited on the described organic luminous layer;
One negative electrode, this cathodic deposition are on described organic electron transport layer, and the area of this negative electrode is less than the area of organic electron transport layer.
The material of wherein said hole injection layer is: transition metal oxide Can Za perylene is a derivant material, and the weight ratio of its transition metal oxide doping content is 10%～50%.
Perylene in the wherein said hole injection layer is that derivant material is following arbitrary material: the perylene that perylene tetracarboxylic acid dianhydride or perylene tetracarboxylic acid imidodicarbonic diamide have electric transmission character is a derivative.
Transition metal oxide in the wherein said hole injection layer is following arbitrary material: molybdenum trioxide, rhenium trioxide or tungstic acid.
The thickness of wherein said hole injection layer is 5～20 nanometers.
The material of described organic cavity transmission layer is following arbitrary material: N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines or N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines.
Described organic light emission layer material is: oxine aluminium-green glow.
The material of described electron transfer layer is following arbitrary material: oxine aluminium or 1,3,5-three (2-N-phenyl benzimidazole) benzene.
Described negative electrode is lithium fluoride/aluminium or silver.
The gross thickness of described hole injection layer and hole transmission layer is 80 nanometers, and the gross thickness of organic luminous layer and electron transfer layer is 60 nanometers, and the thickness of metallic cathode is greater than 120 nanometers.
Description of drawings
In order to further specify content of the present invention, below in conjunction with instantiation and drawings in detail as after, wherein:
Fig. 1 is the structural representation of derivative as the Organic Light Emitting Diode of hole injection structure for a kind of transition metal oxide Can Za perylene that adopts;
Fig. 2 and Fig. 3 are device indium oxide tin glass (ITO)/molybdenum oxide Can Za perylene tetracarboxylic acid dianhydride (MoO
3: PTCDA) (1: X, weight ratio) 10 nanometers/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB), 70 nanometers/oxine aluminium (Alq
3) 60 nanometers/lithium fluoride (LiF), 1 nanometer/aluminium (Al) 120 nanometers (X=2,4,6) and comparative device indium oxide tin glass (ITO)/molybdenum oxide (MoO
3) 10 nanometers/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB), 70 nanometers/oxine aluminium (Alq
3) 60 nanometers/lithium fluoride (LiF), 1 nanometer/aluminium (Al) 120 nanometers and device indium oxide tin glass (ITO)/perylene tetracarboxylic acid dianhydride (PTCDA) 10 nanometers/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB), 70 nanometers/oxine aluminium (Alq
3) photoelectric properties of 60 nanometers/lithium fluoride (LiF), 1 nanometer/aluminium (Al) 120 nanometers.
Embodiment
Involved in the present invention is that a kind of transition metal oxide Can Za perylene that adopts is the Organic Light Emitting Diode of derivative as hole injection structure.For example, such organic LED structure can be formed (consulting shown in Figure 1) by a positive C 1, organic hole implanted layer C2, organic cavity transmission layer C3, an organic luminous layer C4, electron transfer layer C5, a negative electrode C6.
In the present invention, positive C 1 is generally ITO (tin indium oxide) glass, handle 15 minutes to improve the work function of ITO before evaporating the hole injection layer material under the atmosphere of ozone, positive C 1 also can be translucent metal electrode, for example gold, silver, platinum simultaneously.
In the present invention, hole injection layer C2 material be transition metal oxide to mix assorted perylene be derivant material, the perylene of wherein selecting for use is that derivant material can be being that the perylene that perylene tetracarboxylic acid dianhydride (PTCDA), perylene tetracarboxylic acid imidodicarbonic diamide etc. have electric transmission character is a derivative.Transition metal oxide is selected MoO for use
3, ReO
3Or WO
3, their common advantage is that stability is high, doping back cavitation concentration and mobility are high.The perylene is that derivant material and transition metal oxide are evaporated from two sources respectively when hydatogenesis hole injection layer material, evaporation rate according to two kinds of materials of concentration adjustment of required doping causes the deposition rate of doping film to maintain for 1 dust/second to 1.5 dust/seconds greatly.
In the present invention, organic cavity transmission layer C3 material is meant that those possess the organic molecule material of higher hole mobility, preferential conduction hole.Can for,
N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB), N, N '-two (3-aminomethyl phenyl-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (TPD).
In the present invention, organic luminous layer C4 material can send visible light, selects so have widely, and green light material can be selected the 8-hydroxyquinoline aluminum used always, and organic luminous layer can blue light-emitting (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)); It also can be near infrared light (Appl.Phys.Lett.88,071117 (2006)).
In the present invention, organic electron transport layer C5 material is meant that those possess the organic molecule material than high electron mobility, preferential conduction electron.Can for:
Oxine aluminium (Alq
3);
1,3,5-three (2-N-phenyl benzimidazole) benzene (TPBI);
Magnesium (Mg) Can perylene tetracarboxylic acid dianhydride (PTCDA);
Magnesium (Mg) is mixed CuPc (CuPc);
Alkali metal is mixed oxine aluminium (Alq
3) etc.
In the present invention, negative electrode C6 can be silver, lithium fluoride/aluminium, gold.For guaranteeing that the light that luminescent layer is launched does not see through negative electrode, the thickness of evaporation cathode should be greater than 120 nanometers.
Characteristics of the present invention and advantage:
(1) the invention provides a kind of novel organic hole implanted layer material-transition metal oxide Can Za perylene is derivant material, the doping Shi De perylene of transition metal oxide is that derivant material has had good hole injection and transmission performance, make the bright voltage that rises of device reduce, efficient improves.
(2) because the film forming that it is derivative itself that transition metal oxide has good stable perylene is fine, simultaneously hole injection layer has stopped in the anodic oxidation indium tin indium to the infiltration of hole transmission layer, so the thermal stability of device and working life all improve a lot.
Example:
We have prepared a kind of Organic Light Emitting Diode that the present invention relates to, and its device architecture is indium oxide tin glass (ITO)/molybdenum oxide Can Za perylene tetracarboxylic acid dianhydride MoO
3: PTCDA (1: X, weight ratio) 10 nanometers/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB) 70 nanometers/oxine aluminium (Alq
3) 60 nanometers/lithium fluoride (LiF), 1 nanometer/aluminium (Al) 120 nanometers.(X＝2、4、6)。With itself and non-impurity-doped device indium oxide tin glass (ITO)/molybdenum oxide (MoO
3) 10 nanometers/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB) 70 nanometers/oxine aluminium (Alq
3) 60 nanometers/lithium fluoride (LiF), 1 nanometer/aluminium (Al) 120 nanometers and device indium oxide tin glass (ITO)/perylene tetracarboxylic acid dianhydride 10 nanometers/N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines (NPB) 70 nanometers/oxine aluminium (Alq
3) 60 nanometers/lithium fluoride (LiF), 1 nanometer/aluminium (Al) 120 nanometers comparison, Fig. 2 and Fig. 3 have provided the photoelectric properties of these devices.As can be seen, injection of the hole of such device and transmission performance are very good, can send very strong green glow.Simultaneously, for more yet finding of device lifetime, do not have the life-span of doped layer that 2～3 times raising has been arranged the device lifetime that has molybdenum oxide to mix assorted perylene tetracarboxylic acid dianhydride.
Above-mentioned is preferred embodiment of the present invention only, is not in order to limit claim of the present invention; All other do not break away from the equivalence of being finished under the disclosed spirit and changes or modification, all should be included in the claim scope of the present invention.
Claims (10)
1. an Organic Light Emitting Diode that adopts doped metallic oxide as hole injection structure is characterized in that, comprising:
One transparent anode;
One organic hole implanted layer, this organic hole implanted layer is deposited on the described transparent anode, and the area of this organic hole implanted layer is less than the area of transparent anode;
One organic cavity transmission layer, this organic cavity transmission layer are deposited on the described organic hole implanted layer;
One organic luminous layer, this organic light emission are deposited upon on the described organic cavity transmission layer;
One organic electron transport layer, this organic electron transport layer are deposited on the described organic luminous layer;
One negative electrode, this cathodic deposition are on described organic electron transport layer, and the area of this negative electrode is less than the area of organic electron transport layer.
2. employing doped metallic oxide according to claim 1 is as the Organic Light Emitting Diode of hole injection structure, it is characterized in that, the material of wherein said hole injection layer is: transition metal oxide Can Za perylene is a derivant material, and the weight ratio of its transition metal oxide doping content is 10%～50%.
3. employing doped metallic oxide according to claim 2 is as the Organic Light Emitting Diode of hole injection structure, it is characterized in that the perylene in the wherein said hole injection layer is that derivant material is following arbitrary material: the perylene that perylene tetracarboxylic acid dianhydride or perylene tetracarboxylic acid imidodicarbonic diamide have electric transmission character is a derivative.
4. employing doped metallic oxide according to claim 1 is as the Organic Light Emitting Diode of hole injection structure, it is characterized in that the transition metal oxide in the wherein said hole injection layer is following arbitrary material: molybdenum trioxide, rhenium trioxide or tungstic acid.
5. employing doped metallic oxide according to claim 1 is characterized in that as the Organic Light Emitting Diode of hole injection structure the thickness of wherein said hole injection layer is 5～20 nanometers.
6. employing doped metallic oxide according to claim 1 is as the Organic Light Emitting Diode of hole injection structure, it is characterized in that, the material of described organic cavity transmission layer is following arbitrary material: N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines or N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines.
7. employing doped metallic oxide according to claim 1 is characterized in that as the Organic Light Emitting Diode of hole injection structure described organic light emission layer material is: oxine aluminium-green glow.
8. employing doped metallic oxide according to claim 1 is as the Organic Light Emitting Diode of hole injection structure, it is characterized in that, the material of described electron transfer layer is following arbitrary material: oxine aluminium or 1,3,5-three (2-N-phenyl benzimidazole) benzene.
9. employing doped metallic oxide according to claim 1 is characterized in that as the Organic Light Emitting Diode of hole injection structure described negative electrode is lithium fluoride/aluminium or silver.
10. employing doped metallic oxide according to claim 1 is as the Organic Light Emitting Diode of hole injection structure, it is characterized in that, the gross thickness of described hole injection layer and hole transmission layer is 80 nanometers, the gross thickness of organic luminous layer and electron transfer layer is 60 nanometers, and the thickness of metallic cathode is greater than 120 nanometers.
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| GB2486203A (en) * | 2010-12-06 | 2012-06-13 | Cambridge Display Tech Ltd | Transition metal oxide doped interface by deposition and drying of precursor |
| CN102640318A (en) * | 2010-11-29 | 2012-08-15 | 松下电器产业株式会社 | Method of producing organic light-emitting diode, organic light-emitting diode, luminescent device, display panel, and display device |
| CN102683609A (en) * | 2011-03-14 | 2012-09-19 | 海洋王照明科技股份有限公司 | Inverted transparent organic electroluminescent device and manufacturing method thereof |
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| CN102640318A (en) * | 2010-11-29 | 2012-08-15 | 松下电器产业株式会社 | Method of producing organic light-emitting diode, organic light-emitting diode, luminescent device, display panel, and display device |
| CN102640318B (en) * | 2010-11-29 | 2015-12-16 | 株式会社日本有机雷特显示器 | The manufacture method of organic illuminating element, organic illuminating element, light-emitting device, display floater and display unit |
| US9390921B2 (en) | 2010-12-06 | 2016-07-12 | Cambridge Display Technology Limited | Adhesion layer for solution-processed transition metal oxides on inert metal contacts |
| GB2486203A (en) * | 2010-12-06 | 2012-06-13 | Cambridge Display Tech Ltd | Transition metal oxide doped interface by deposition and drying of precursor |
| CN102683609A (en) * | 2011-03-14 | 2012-09-19 | 海洋王照明科技股份有限公司 | Inverted transparent organic electroluminescent device and manufacturing method thereof |
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| CN104183774A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic light emitting device and manufacturing method thereof |
| CN104993064A (en) * | 2015-07-29 | 2015-10-21 | 苏州大学 | Short-circuit-preventing transparent OLED device and preparing method thereof |
| CN105374953A (en) * | 2015-12-24 | 2016-03-02 | Tcl集团股份有限公司 | QLED and preparation method thereof as well as luminous module and display device |
| CN105374953B (en) * | 2015-12-24 | 2019-01-04 | Tcl集团股份有限公司 | A kind of light emitting diode with quantum dots and preparation method, illuminating module and display device |
| CN109599413A (en) * | 2017-09-30 | 2019-04-09 | 上海和辉光电有限公司 | A kind of display panel and display device |
| CN109599413B (en) * | 2017-09-30 | 2021-04-27 | 上海和辉光电股份有限公司 | Display panel and display device |
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Open date: 20100811 |