CN1783532A - Organic el device and method of manufacturing the same - Google Patents
Organic el device and method of manufacturing the same Download PDFInfo
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- CN1783532A CN1783532A CNA2005101315071A CN200510131507A CN1783532A CN 1783532 A CN1783532 A CN 1783532A CN A2005101315071 A CNA2005101315071 A CN A2005101315071A CN 200510131507 A CN200510131507 A CN 200510131507A CN 1783532 A CN1783532 A CN 1783532A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
Abstract
An organic electroluminescent device is disclosed that includes an emission layer between a first electrode and a second electrode, and a buffer layer between the emission layer and the first electrode. The buffer layer includes a carbon-based compound and may be about 0.1 nm to about 100 nm thick. The organic electroluminescent device has greater driving voltage, better efficiency, and a longer life expectancy. while the color coordinate of the blue, green, and red does not change.
Description
Background technology
The application requires to submit in the korean patent application 10-2004-0081114 on October 11st, 2004 and submit in the interests of the korean patent application 10-2005-0071502 on August 4th, 2005 in Korea S Department of Intellectual Property, is incorporated herein by reference in full at this.
1. technical field
The present invention relates to a kind of Organnic electroluminescent device and preparation method thereof, more particularly, the present invention relates to a kind of el light emitting device and preparation method thereof with long-life and low-power consumption.
2. the explanation of correlation technique
Organic electroluminescent (EL) device is spontaneous emission.That is to say that when voltage put on the organic layer that is inserted between anode and the negative electrode, electronics and hole be in the organic layer combination, thereby luminous.Organic El device can be used for forming information display device, and it has high resolution, fast response time, wide visual angle, light and thin.Organic El device has purposes widely, comprises mobile phone, high end message display unit or the like.
Organic El device has developed so far: in industrial market and sphere of learning and Thin Film Transistor-LCD (TFT-LCD) competition.But there is the problem of the development of its high-quality of many preventions, large-scale production in organic El device, as inefficient, the life-span is short and power consumption is high.These problems must solve.
Summary of the invention
The invention provides a kind of the qualification under the luminescent material type, have organic electroluminescent (EL) device of low driving voltage, it makes power consumption reduce and the life-span increases.
The present invention also provides a kind of method for preparing described organic El device, and this method comprises that formation is by the resilient coating that forms based on carbon compound.Under this kind situation, by the thickness of control resilient coating, the efficient of organic El device and life-span can further improve.
According to an aspect of the present invention, provide a kind of Organnic electroluminescent device, it comprises the emission layer that is inserted between first electrode and second electrode; This Organnic electroluminescent device comprises that by the thickness that forms based on carbon compound be the resilient coating of 0.1nm-100nm between the emission layer and first electrode.
According to another aspect of the present invention, a kind of method for preparing organic El device is provided, this device comprises the emission layer that is inserted between first electrode and second electrode, and this method is included in and forms by the thickness that forms based on carbon compound between the emission layer and first electrode is the resilient coating of 0.1nm-100nm.
Provide a kind of organic El device more on the other hand according to of the present invention, it comprises substrate; Be formed on suprabasil first electrode; Be formed on the hole injection layer on first electrode; Be formed on the emission layer on the hole injection layer; Second electrode with being formed on the emission layer wherein is inserted between first electrode and the hole injection layer by the resilient coating that forms based on carbon compound.
Described organic El device can also comprise the hole transmission layer that is formed between hole injection layer and the emission layer, and is formed between hole injection layer and the hole transmission layer by the resilient coating that forms based on carbon compound.In addition, when being formed between first electrode and hole injection layer by the resilient coating that forms based on carbon compound, this hole injection layer can be used based on carbon compound and mix.
In described hole injection layer and the hole transmission layer at least one can be by forming based on carbon compound.Based on every layer of 100 weight portions, describedly can be the 0.005-99.95 weight portion based on the carbon compound amount.
Described organic El device can also comprise the one deck at least that is selected from hole blocking layer (hole blocking layer), electron transfer layer and electron injecting layer that is inserted between the emission layer and second electrode.
According to another aspect of the present invention, provide a kind of organic El device, it comprises: substrate; Be formed on suprabasil first electrode; Be formed on the hole transmission layer on first electrode; Be formed on the emission layer on the hole transmission layer; Second electrode with being formed on the emission layer wherein is inserted between first electrode and the hole transmission layer by the resilient coating that forms based on carbon compound.
Described organic El device can also be included in the one deck at least that is selected from hole blocking layer (hole blocking layer), electron injecting layer and electron transfer layer between the emission layer and second electrode.
According to another aspect of the present invention, provide a kind of organic El device, it comprises: substrate; Be formed on suprabasil first electrode; Be formed on the hole injection layer on first electrode; Be formed on the hole transmission layer on the hole injection layer; Be formed on the emission layer on the hole transmission layer; With second electrode that is formed on the emission layer, and be inserted between hole injection layer and the hole transmission layer by the resilient coating that forms based on carbon compound.
This organic El device can also be included in electron injecting layer between the electron transfer layer and second electrode and the one deck at least in the hole blocking layer.
Brief description of drawings
Above-mentioned and further feature of the present invention and advantage will become more clear with reference to the explanation of accompanying drawing by concrete exemplary.Wherein:
Fig. 1-5 is the sectional view according to the organic El device of embodiment of the present invention; With
Fig. 6 is the structure that is used for C60 fullerene of the present invention.
Detailed Description Of The Invention
Organic electroluminescent (EL) device according to one embodiment of the invention comprises the emission layer that is inserted between the first electrode and the second electrode, and is inserted between the first electrode and the emission layer by the cushion that forms based on carbon compound.
This organic El device can also be included in the hole injection layer between the first electrode (anode) and the emission layer, in this structure, described cushion can be formed between the first electrode and the hole injection layer, between hole injection layer and the emission layer or not only between the first electrode and the hole injection layer but also between hole injection layer and emission layer.
In addition, this organic El device can also comprise the hole transmission layer that is inserted between the first electrode and the emission layer, in this structure, described cushion can be formed between the first electrode and the hole transmission layer, between hole transmission layer and the emission layer or not only between the first electrode and the hole transmission layer but also between hole transmission layer and emission layer.
In addition, this organic El device can also comprise that order is formed on hole injection layer and the hole transmission layer between the first electrode and the emission layer, in this structure, described cushion can be formed between in the combination of the first electrode and hole injection layer, hole injection layer and hole transmission layer and hole transmission layer and emission layer at least one.
As mentioned above, by between the first electrode and emission layer, comprising by the cushion that forms based on carbon compound, the form of the organic El device of this form of film can not change, the color coordinates of this organic El device can not change yet, simultaneously, change as the ITO electrode of the first electrode and the interface energy band gap between the hole injection layer so that the hole easier from the ITO electrode injection to hole injection layer, thereby reduced driving voltage. In addition, firmly be formed on as the ITO electrode of the first electrode and the long-life that the cushion between the hole injection layer helps described organic El device.
The thickness of described cushion can be 0.1-100nm, preferred 1-10nm, more preferably 5-8nm. When the thickness of cushion was lower than 0.1nm, the characteristic of Organnic electroluminescent device can not be improved. When the thickness of cushion during greater than 100nm, the characteristic of Organnic electroluminescent device, can improve such as the life-span, contrast etc., but the width of driving voltage voltage drop can reduce by width saturated or voltage gain.
As mentioned above, comprise by the cushion that forms based on carbon compound such as fullerene that according to the organic El device of one embodiment of the invention it is inserted between the first electrode and the hole injection layer, between hole injection layer and the hole transmission layer and/or between the first electrode and hole transmission layer. Perhaps, by the cushion that forms based on carbon compound can be formed between the first electrode and the hole injection layer, between the first electrode and the hole transmission layer and/or between hole injection layer and hole transmission layer. In this kind situation, described hole injection layer and/or hole transmission layer are used based on carbon compound and are mixed. Perhaps, electron transfer layer is used based on carbon compound and is mixed. Perhaps, the cushion based on carbon compound of mixing is formed between the first electrode and the hole injection layer and/or between the first electrode and hole transmission layer, and electron transfer layer is used based on carbon compound and mixed.
Described based on carbon compound without limits, but can be the complex based on carbon that contains metal, namely, contain the allotrope of carbon of 60-500 carbon atom and the complex of metal. Can be selected from following compound at least a based on carbon compound: fullerene, the fullerene complex that contains metal, CNT, carbon fiber, carbon black, graphite, Cabbeen carbon (carbine), MgC60, CaC60 and SrC60. The described fullerene with structure shown in Figure 6 that is preferably based on carbon compound.
Fullerene (being also referred to as bucky-ball (buckyballs)) forms by following manner: use in a vacuum strong laser irradiation graphite, so that the carbon atom that carbon atom separates and separates from graphite surface is in conjunction with forming a kind of new structure. The example of fullerene comprises the C60 that 60 carbon atoms form, C70, C76, C84 etc.
Simultaneously, comprising based on carbon compound that as the ITO electrode of anode and the cushion between the hole injection layer described hole injection layer and/or hole transmission layer or electron transfer layer can be doped with based on carbon compound. Based on described hole injection layer, hole transmission layer or the electron transfer layer of 100 weight portions, should be based on the carbon compound 0.005-99.95 weight portion that can mix. When the usefulness based on carbon compound measured from above-mentioned scope, the raising of the performance of organic El device was just insignificant.
Fig. 1-5 is the sectional view according to the organic El device of embodiment of the present invention.
With reference to Fig. 1, first electrode 10 is deposited in the substrate 20, and hole injection layer 11 is deposited on first electrode 10, and emission layer 12 and second electrode 13 are deposited on the hole injection layer 11 successively.Be inserted between first electrode 10 and the hole injection layer 11 by the resilient coating 14 that forms based on carbon compound.Described hole injection layer 11 can be used based on carbon compound and mix.
With reference to Fig. 2, this organic El device comprises: be deposited on first electrode 10 in the substrate 20; Be deposited on hole injection layer 11 and hole transmission layer 16 on first electrode 10 successively; Be deposited on successively on the hole transmission layer 16 and the emission layer 12 and second electrode 13; And be inserted between hole injection layer 11 and the hole transmission layer 16 by the resilient coating 14 that forms based on carbon compound.
Organic El device shown in Figure 3 has and the identical structure of the described organic El device of Fig. 1, except hole transmission layer 16 is inserted between hole injection layer 11 and the emission layer 12.
Organic El device shown in Figure 4 comprises first electrode 10 that is deposited in the substrate 20, be deposited on successively on first electrode 10 by resilient coating 12 that forms based on carbon compound and hole transmission layer 14, and be deposited on the emission layer 12 and second electrode 13 on the hole transmission layer 14 successively.
Organic El device shown in Figure 5 has and the identical structure of the described organic El device of Fig. 3, and different is that electron transfer layer 17 and electron injecting layer 18 are formed between the emission layer 12 and second electrode 13 successively.Hole injection layer 11 and/or hole transmission layer 16 or electron transfer layer 17 can be used based on carbon compound and mix.
Organic El device according to embodiment of the present invention can also comprise hole blocking layer or the intermediate layer that is used for improving the interface layer performance, and they do not show in the drawings.
Preparation will be described below according to the method for the organic El device of embodiment of the present invention shown in Figure 5.
Described first electrode 10 can be formed by conducting metal or its oxide, and it makes the hole be easy to be injected on first electrode 10.Described conducting metal or its oxide can for indium tin oxide (Lindium TinOxide) (ITO), indium-zinc oxide (Lindium Zinc Oxide) (IZO), nickel, platinum, gold or iridium or the like.
The substrate of gained uses the organic solvent such as isopropyl alcohol (IPA) and acetone to clean, and uses the UV/ ozone treatment then.
In addition, resilient coating 12 can form the thickness of 1nm-10nm with the deposition rate of 0.01-0.2nm/s under vacuum condition.Particularly, when resilient coating 12 formed the thickness of 1-5nm, deposition rate can be 0.01-0.05nm/s.When resilient coating 12 formed the thickness of 5-10nm, deposition rate can be 0.05-0.2nm/s.Resilient coating with above-mentioned deposition rate forms efficient and the life-span that has influenced organic El device, and this should be because morphologic slight change is caused.This situation can be confirmed in following embodiment and Comparative Examples.
Subsequently, hole-injecting material is by vacuum heat deposition or be spin-coated on the resilient coating 14 and form hole injection layer 11.Described hole injection layer 11 has reduced the contact resistance between first electrode 10 and the emission layer and has increased from the cavity transmission ability of first electrode, 10 past emission layers.Thereby the driving voltage of this organic El device reduces, and the life-span of this organic El device increases.
[formula 3]
Hole mobile material is by vacuum heat deposition or be spin-coated on according to the method described above on the hole injection layer 11 that forms, and has formed hole transmission layer 16.Described hole mobile material can be N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-[1, the 1-xenyl]-4,4 '-diamines (TPD), N, N '-two (naphthalene 1-yl)-N, N '-diphenylbenzidine (α-NPD), IDE320 (deriving from Idmitz Co.) or the like, but be not limited to this.The thickness of hole transmission layer 11 can be 10-40nm.When the thickness of hole transmission layer 11 is lower than 10nm, cavity transmission ability is reduced, this is undesirable.When the thickness of hole transmission layer 11 during greater than 40nm, the driving voltage of device increases, and this also is undesirable.
[formula 4]
Then, by vacuum heat deposition or spin coating, on hole transmission layer 16, form emission layer 12.
Described emission layer 12 can have the thickness of 15-60nm, is preferably 30-50nm.When emission layer 12 thickenings, the driving voltage of device increases.Thereby thickness can not be used in the organic El device greater than the emission layer 12 of 60nm.
Randomly, hole blocking layer (not showing among Fig. 5) can also be formed on the emission layer 12.This hole blocking layer forms by vacuum moulding machine hole barrier materials on emission layer 12, perhaps by forming with hole barrier materials spin coating emission layer 12.Described hole barrier materials can have electron transport ability, and its ionization potential is greater than the ionization potential of emissive material.Described hole barrier materials can for two (2-methyl-oxines)-(right-phenyl phenol)-aluminium (Balq), bathocuproine (BCP), three (N-aryl benzimidazole) (TPBI) etc., but be not limited to this.The thickness of hole blocking layer can be 3-7nm.When the thickness of hole blocking layer was lower than 3nm, the hole barrier ability can die down, and this is undesirable.When hole barrier layer thickness during greater than 7nm, the driving voltage of device increases, and this also is undesirable.
According to embodiment of the present invention, can be inserted between anode 10 and the hole injection layer 11 by the resilient coating 14 that forms based on carbon compound.In addition, hole injection layer 11 and/or hole transmission layer 16 or electron transfer layer 17 can be used based on carbon compound and mix.
That is to say, be deposited on based on carbon compound and form resilient coating 14 between anode 10 and the hole injection layer 11; And hole injection layer 11 and/or hole transmission layer 16 or electron transfer layer 17 form by hole-injecting material, hole mobile material or electron transport material and based on the hot codeposition of the vacuum of carbon compound.Based on hole injection layer, hole transmission layer or the electron transfer layer of 100 weight portions, be the 0.005-99.95 weight portion based on the content of carbon compound.
The thickness of electron transfer layer 17 can be 15-60nm.When the thickness of electron transfer layer 17 was lower than 15nm, electron transport ability descended, and this is undesirable.When the thickness of electron transfer layer 17 during greater than 60nm, driving voltage increases, and this also is undesirable.
In addition, electron injecting layer 18 can randomly be formed on the electron transfer layer 17.Described electron injecting layer 18 can be by LiF, NaCl, CsF, Li
2Formation such as O, BaO, Liq.The thickness of electron injecting layer 18 is 0.5-2nm.When the thickness of electron injecting layer 18 was lower than 0.5nm, the electronics injectability descended, and this is undesirable.When the thickness of electron injecting layer 18 during greater than 2nm, driving voltage increases, and this also is undesirable.
Then, the cathodic metal vacuum heat deposition forms negative electrode on electron injecting layer 18, Here it is second electrode 13.As a result, organic El device is completed into.
Described cathodic metal can be Li, Mg, Al, Al-Li, Ca, Mg-In, Mg-Ag etc.
Organic El device comprises anode, hole injection layer, hole transmission layer, emission layer, electron transfer layer, electron injecting layer, negative electrode according to embodiments of the present invention, and if desired, can also comprise one or two intermediate layer.In addition, described organic El device can also comprise electronic barrier layer.
The present invention describes more specifically with reference to following embodiment.Following embodiment is used for the present invention is illustrated, but is not used in the scope of the present invention that limits.
Embodiment 1
15 Ω/cm of Corning Co will be derived from
2Substrate of glass (120nm) is cut into the size of 50mm * 50mm * 0.7mm, with ultrasonic waves for cleaning 5 minutes, with ultrasonic waves for cleaning 5 minutes, and uses UV and ozone clean 30 minutes in pure water in isopropyl alcohol.Gains are as anode.In the preparation method of organic El device, the ito glass substrate of cleaning plasma treatment 9 minutes under the pressure of 0.1 millitorr.
Buckminster fullerene (C60) is 10
-6Be deposited on the deposition rate of 0.01nm/s under the pressure of holder that to form thickness in the substrate be the resilient coating of 3nm.Then, IDE406 (deriving from Idemitz Co.) vacuum heat deposition forms the hole injection layer that thickness is 70nm on resilient coating.Then, the NPD vacuum heat deposition forms the hole transmission layer that thickness is 15nm on hole injection layer.
Subsequently, the Alq3 vacuum heat deposition that is doped with C545T forms the green emitted layer of the about 35nm of thickness on hole transmission layer.Then, be deposited on as the Alg3 of electron transport material that to form thickness on the emission layer be the electron transfer layer of 25nm.
The LiF vacuum moulding machine is deposited at the electron injecting layer that forms 1nm thickness on the electron transfer layer and Al that to form thickness on the electron injecting layer be the negative electrode of 80nm, thereby has formed the LiF/Al electrode.As a result, prepare organic El device.
Embodiment 2
15 Ω/cm of Corning Co will be derived from
2Substrate of glass (120nm) is cut into the size of 50mm * 50mm * 0.7mm, with ultrasonic waves for cleaning 5 minutes, with ultrasonic waves for cleaning 5 minutes, and uses UV and ozone clean 30 minutes in pure water in isopropyl alcohol.Gains are as anode.In the preparation method of organic El device, the ito glass substrate of cleaning plasma treatment 9 minutes under the pressure of 0.1 millitorr.
Buckminster fullerene (C60) is 10
-6Be deposited on the deposition rate of 0.05nm/s under the pressure of holder that to form thickness in the substrate be the resilient coating of 3nm.Then, NPD vacuum heat deposition thickness on resilient coating is that 15nm forms hole transmission layer.
Subsequently, the Alq3 vacuum heat deposition that is doped with C545T forms the green emitted layer of the about 35nm of thickness on hole transmission layer.Then, be deposited on as the Alg3 of electron transport material that to form thickness on the emission layer be the electron transfer layer of 25nm.
The LiF vacuum moulding machine forms the electron injecting layer of 1nm thickness on electron transfer layer, and Al is deposited on the electron injecting layer that to form thickness be the negative electrode of 80nm, thereby has formed the LiF/Al electrode.As a result, prepare organic El device.
Embodiment 3
Prepare organic El device with the method identical, except the deposition rate with 0.1nm/s is the thickness of 3nm with buffer layer deposition with embodiment 1.
Embodiment 4
Prepare organic El device with the method identical, except the deposition rate with 0.2nm/s is the thickness of 3nm with buffer layer deposition with embodiment 2.
Embodiment 5
Prepare organic El device with the method identical, except the deposition rate with 0.01nm/s is the thickness of 7nm with buffer layer deposition with embodiment 1.
Embodiment 6
Prepare organic El device with the method identical, except the deposition rate with 0.05nm/s is the thickness of 7nm with buffer layer deposition with embodiment 2.
Embodiment 7
Prepare organic El device with the method identical, except the deposition rate with 0.1nm/s is the thickness of 7nm with buffer layer deposition with embodiment 1.
Embodiment 8
Prepare organic El device with the method identical, except the deposition rate with 0.2nm/s is the thickness of 7nm with buffer layer deposition with embodiment 2.
The comparative example 1
Prepare organic El device with the method identical, except the deposition rate with 0.05nm/s is the thickness of 15nm with buffer layer deposition with embodiment 1.
The comparative example 2
Prepare organic El device with the method identical, except the deposition rate with 0.05nm/s is the thickness of 15nm with buffer layer deposition with embodiment 2.
The comparative example 3
Prepare organic El device with the method identical, except the deposition rate with 0.05nm/s is the thickness of 30nm with buffer layer deposition with embodiment 1.
The comparative example 4
Prepare organic El device with the method identical, except the deposition rate with 0.3nm/s is the thickness of 30nm with buffer layer deposition with embodiment 2.
Test embodiment 1
According to following method, driving voltage, efficient (current density) and the half-life of the organic El device of test implementation example 1-8 and comparative example 1-4 preparation, test result sees Table 1.
Brightness: use BM5A (Topcon Co.) test
Driving voltage: use the 238HIGH CURRENT SOURCEMEASURE UNIT test that derives from Keithley Co..
Current density: at 10-100mA/cm
2In the scope, when direct current (DC) with 10mA/cm
2During increase, test 9 or more point of each device.
Half-life: at DC is 50mA/cm
2Down, when the initial brightness of each organic El device be reduced to it 50% the time, measure the time that needs.Use at least three identical device to test reproducibilitys.
Table 1
| Deposition rate (nm/s) | Buffer layer thickness (nm) | Driving voltage (V) | Efficient (cd/v) | Half-life (h) | |
| Embodiment 1 | 0.01 | 3 | 6.3 | 14 | 1500 |
| Embodiment 2 | 0.05 | 3 | 6.2 | 13 | 1500 |
| Embodiment 3 | 0.1 | 3 | 6.1 | 13 | 1000 |
| Embodiment 4 | 0.2 | 3 | 6.0 | 12 | 1000 |
| Embodiment 5 | 0.01 | 7 | 9.2 | 17 | 1100 |
| Embodiment 6 | 0.05 | 7 | 8.4 | 16 | 1000 |
| Embodiment 7 | 0.1 | 7 | 6.1 | 14 | 1500 |
| Embodiment 8 | 0.2 | 7 | 6.0 | 14 | 1500 |
| The comparative example 1 | 0.05 | 15 | 9.4 | 14 | 900 |
| The comparative example 2 | 0.05 | 25 | 10.2 | 16 | 900 |
| The comparative example 3 | 0.05 | 30 | 11.0 | 15 | 900 |
| The comparative example 4 | 0.3 | 30 | 10.9 | 15 | 900 |
With reference to table 1, the comparison of the organic El device of embodiment 1-8 has lower driving voltage, better luminous efficiency and longer life-span than the organic El device of embodiment 1-4 as can be seen.
Embodiment 9
The substrate of glass that will have the ITO electrode (derives from Corning Co, sheet resistance 15 Ω/cm
2, thickness is 120nm) and be cut into the size of 50mm * 50mm * 0.7mm, in isopropyl alcohol,, in pure water,, and used UV and ozone clean 30 minutes with ultrasonic waves for cleaning 5 minutes with ultrasonic waves for cleaning 5 minutes, gains are as anode.The substrate of glass that has the ITO electrode that obtains plasma treatment 9 minutes under 0.1 millitorr or lower pressure.
Buckminster fullerene vacuum heat deposition forms thickness in the substrate that plasma treatment is crossed be the resilient coating of 1nm.Subsequently, IDE406 (deriving from Idemitz Co.) vacuum heat deposition forms the hole injection layer that thickness is 70nm on resilient coating.Then, the NPD vacuum heat deposition forms the hole transmission layer that thickness is 15nm on hole injection layer.
IDE 140 (Idemitz Co.) vacuum heat deposition forms the blue emission layer that thickness is about 30nm on hole transmission layer.Then, be deposited on as the Alg3 of electron transport material that to form thickness on the emission layer be the electron transfer layer of 25nm.
The LiF vacuum moulding machine forms the electron injecting layer of 1nm thickness on electron transfer layer, and Al is deposited on the electron injecting layer that to form thickness be the negative electrode of 80nm, thereby has formed the LiF/Al electrode.As a result, prepare organic El device.
Embodiment 10-14
Prepare organic El device with the method identical, except resilient coating has 2,3.5,5,6.5 or the thickness of 8nm respectively with embodiment 9.
Embodiment 15
The substrate of glass that will have the ITO electrode (derives from Corning Co, sheet resistance 15 Ω/cm
2, thickness is 120nm) and be cut into the size of 50mm * 50mm * 0.7mm, in isopropyl alcohol,, in pure water,, and used UV and ozone clean 30 minutes with ultrasonic waves for cleaning 5 minutes with ultrasonic waves for cleaning 5 minutes, gains are as anode.The ito glass substrate that obtains plasma treatment 9 minutes under 0.1 millitorr and lower pressure.
Buckminster fullerene vacuum heat deposition forms thickness in the substrate that plasma treatment is crossed be the resilient coating of 5nm.Subsequently, IDE406 (deriving from Idemitz Co.) vacuum heat deposition forms the hole injection layer that thickness is 70nm on resilient coating.Then, the NPD vacuum heat deposition forms the hole transmission layer that thickness is 15nm on hole injection layer.
C545T and Alq3 codeposition form the green emitted layer of the about 35nm of thickness on hole transmission layer, then, be deposited on as the Alq3 of electron transport material that to form thickness on the green emitted layer be the electron transfer layer of 25nm.
The LiF vacuum moulding machine forms the electron injecting layer of 1nm thickness on electron transfer layer, and Al is deposited on the electron injecting layer that to form thickness be the negative electrode of 100nm, thereby has formed the LiF/Al electrode.As a result, prepare organic El device.
Prepare organic El device according to embodiment 15 identical methods, except resilient coating has 6.5 and the thickness of 8nm respectively.
The substrate of glass that will have the ITO electrode (derives from Corning Co, sheet resistance 15 Ω/cm
2, thickness is 120nm) and be cut into the size of 50mm * 50mm * 0.7mm, in isopropyl alcohol,, in pure water,, and used UV and ozone clean 30 minutes with ultrasonic waves for cleaning 5 minutes with ultrasonic waves for cleaning 5 minutes.Gains are as anode.The ito glass substrate that obtains plasma treatment 9 minutes under 0.1 millitorr and lower pressure.
Buckminster fullerene vacuum heat deposition forms thickness in the substrate that plasma treatment is crossed be the resilient coating of 5nm.Subsequently, IDE406 (deriving from Idemitz Co.) vacuum heat deposition forms the hole injection layer that thickness is 70nm on resilient coating.Then, the NPD vacuum heat deposition forms the hole transmission layer that thickness is 15nm on hole injection layer.
DCJTB and Alq3 codeposition form the red emission layer of the about 35nm of thickness on hole transmission layer.Then, be deposited on as the Alq3 of electron transport material that to form thickness on the red emission layer be the electron transfer layer of 25nm.
LiF vacuum moulding machine 1nm thickness on electron transfer layer forms electron injecting layer, and Al is deposited on that thickness is that 100nm forms negative electrode on the electron injecting layer, thereby has formed the LiF/Al electrode.As a result, prepare organic El device.
Prepare organic El device with the method identical, except resilient coating has 6.5 and the thickness of 8nm respectively with embodiment 15.
The comparative example 5
Prepare organic El device with the method identical, except not forming resilient coating with embodiment 9.
The comparative example 6
Prepare organic El device with the method identical, except not forming resilient coating with embodiment 15.
The comparative example 7
Prepare organic El device with the method identical, except not forming resilient coating with embodiment 18.
Mensuration is according to driving voltage, efficient and the half-life of the organic El device of embodiment 9-14 and comparative example's 5 preparations.The results are shown in shown in the following table 2.
1) initial characteristic
Use BM5A (deriving from Topcon Co.) test brightness, and use 238HIGH CURRENTSOURCE MEASURE UNIT (deriving from Keithley) test driving voltage.Be applied to direct current on the equipment (DC) density at 10-100mA/cm
2Scope in, and with 10mA/cm
2Increase.Each equipment is tested 9 points at least.The reproducibility test is more than 9 times, and the deviation of initial characteristic is 5% or littler.
2) half-life
At DC is 50mA/cm
2Obtain the half-life by the time of measuring initial luminance loss to 50% down.Measure the reproducibility in the life-span of at least three devices with same structure.
Table 2
| The comparative example 5 | Embodiment 9 | | | | | | |
| Buffer layer thickness (nm) | 0 | 10 | 20 | 35 | 50 | 65 | 80 |
| Driving voltage (V) | 9.06 | 7.76 | 7.39 | 7.22 | 7.13 | 6.99 | 6.9 |
| Efficient (cd/A) | 10.48 | 9.64 | 9.48 | 9.56 | 9.93 | 9.56 | 9.61 |
| Half-life (h) | 600 | 800 | 750 | 750 | 850 | 940 | 800 |
With reference to table 2, although as can be seen according to the efficient of the organic El device of embodiment 9-14 with according to comparative example 5 organic El device much at one, but according to the driving voltage of the organic El device of embodiment 9-14 is about 80% according to the driving voltage of comparative example 5 organic El device, and according to the life-span beguine of the organic El device of the embodiment 9-14 life-span long 50% according to comparative example 6 organic El device.
Measurement is according to driving voltage, efficient and the half-life of embodiment 15-17 and comparative example's 6 organic El device.The results are shown in Table 3.
Table 3
| The comparative example 6 | Embodiment 15 | | | |
| Buffer layer thickness (nm) | 0 | 50 | 65 | 80 |
| Driving voltage (V) | 9.6 | 7.6 | 7.52 | 7.61 |
| Efficient (cd/A) | 23.66 | 21.59 | 21.95 | 22.06 |
| Half-life (h) | 650 | 750 | 820 | 720 |
With reference to table 3, although according to the organic El device of embodiment 15-17 with according to the efficient of comparative example 6 organic El device much at one, but according to the driving voltage of the organic El device of embodiment 15-17 is about 80% according to the driving voltage of comparative example 6 organic El device, and according to life-span of the organic El device of embodiment 15-17 be according to 25% of life-span of comparative example 6 organic El device.
Measurement is according to driving voltage, efficient and the half-life of embodiment 18-20 and comparative example's 7 organic El device.The results are shown in Table 4.
Table 4
| The comparative example 7 | | Embodiment 19 | | |
| Buffer layer thickness (nm) | 0 | 50 | 65 | 80 |
| Driving voltage (V) | 7.61 | 5.78 | 5.72 | 5.77 |
| Efficient (cd/A) | 5.62 | 5.16 | 5.65 | 4.98 |
| Half-life (h) | 1500 | 1800 | 1800 | 1500 |
With reference to table 4, although according to the organic El device of embodiment 18-20 with according to the efficient of comparative example 7 organic El device much at one, but according to the driving voltage of the organic El device of embodiment 18-20 is about 80% according to the driving voltage of comparative example 7 organic El device, and according to the life-span beguine of the organic El device of the embodiment 18-20 life-span long 20% according to comparative example 7 organic El device.
In order to obtain bigger driving voltage and longer life-span, comprise by based on carbon compound according to the organic El device of embodiment of the present invention, form as fullerene, be inserted in the resilient coating between first electrode and the emission layer.In addition, the thickness of the deposition rate control resilient coating by using resilient coating, efficient and the life-span that can further improve described organic El device.
Especially, in order to increase driving voltage and to increase the life-span and do not change blueness, green and red color coordinates, organic El device according to embodiment of the present invention comprises: i) by based on carbon compound, as the resilient coating that fullerene etc. forms, it is inserted between first electrode and the hole injection layer, between hole injection layer and the hole transmission layer and/or between first electrode layer and hole transmission layer; Ii) be inserted between first electrode and the hole injection layer, between first electrode and the hole transmission layer and/or the resilient coating between hole injection layer and hole transmission layer, wherein hole injection layer and/or hole transmission layer are used based on carbon compound and are mixed; Iii) be doped with electron transfer layer based on carbon compound; Perhaps iv) be inserted between first electrode and the hole injection layer, between first electrode and the hole transmission layer and/or the resilient coating between hole injection layer and hole transmission layer, wherein electron transfer layer is used based on carbon compound and is mixed.
Although the present invention has carried out special demonstration and description with reference to specific embodiment, but those skilled in the art can understand in not deviating from the scope that the present invention spirit and following claim stipulate, can make change on various forms and the details to the present invention.
Claims (40)
1, a kind of Organnic electroluminescent device that is inserted in the emission layer between first electrode and second electrode that comprises, this Organnic electroluminescent device comprises: between the emission layer and first electrode, be the resilient coating of 0.1nm-100nm by the thickness that forms based on carbon compound.
2, the Organnic electroluminescent device of claim 1 also is included in the hole injection layer between first electrode and the emission layer, and wherein said resilient coating is formed between first electrode and the hole injection layer or between hole injection layer and emission layer.
3, the Organnic electroluminescent device of claim 1 also is included in the hole transmission layer between first electrode and the emission layer, and wherein said resilient coating is formed between first electrode and the hole transmission layer or between hole transmission layer and emission layer.
4, the Organnic electroluminescent device of claim 1, also comprise the hole injection layer and the hole transmission layer that are formed on successively between first electrode and the emission layer, wherein said resilient coating is formed between in the combination of first electrode and hole injection layer, hole injection layer and hole transmission layer and hole transmission layer and emission layer at least one.
5, the Organnic electroluminescent device of claim 1, at least a compound that wherein comprises the complex that is selected from fullerene, contains metal, carbon nano-tube, carbon fiber, carbon black, graphite, Cabbeen carbon, MgC60, CaC60, SrC60, and at least two kinds of described compounds based on fullerene based on carbon compound.
6, the Organnic electroluminescent device of claim 1 between the emission layer and second electrode, also comprises the one deck at least that is selected from hole blocking layer, electron transfer layer and the electron injecting layer.
7, a kind of Organnic electroluminescent device, it comprises:
Substrate;
Be formed on suprabasil first electrode;
Be formed on the hole injection layer on first electrode;
Be formed on the emission layer on the hole injection layer; And
Be formed on second electrode on the emission layer, wherein
Be inserted between first electrode and the hole injection layer by the resilient coating that forms based on carbon compound.
8, the Organnic electroluminescent device of claim 7 wherein comprises at least a compound of the complex based on fullerene, carbon nano-tube, carbon fiber, carbon black, graphite, Cabbeen carbon, MgC60, CaC60 and the SrC60 that are selected from fullerene, contain metal based on carbon compound.
9, the Organnic electroluminescent device of claim 7 also comprises the hole transmission layer that is inserted between hole injection layer and the emission layer.
10, the Organnic electroluminescent device of claim 3, also be included between hole injection layer and the hole transmission layer by the resilient coating that forms based on carbon compound.
11, the Organnic electroluminescent device of claim 10 wherein comprises at least a compound of the complex based on fullerene, carbon nano-tube, carbon fiber, carbon black, graphite, Cabbeen carbon, MgC60, CaC60 and the SrC60 that are selected from fullerene, contain metal based on carbon compound.
12, the Organnic electroluminescent device of claim 7, wherein the thickness of resilient coating is 0.1-100nm.
13, the Organnic electroluminescent device of claim 7 between the emission layer and second electrode, also comprises the one deck at least that is selected from hole blocking layer, electron transfer layer and the electron injecting layer.
14, the Organnic electroluminescent device of claim 7, wherein based on the hole injection layer of 100 weight portions, hole injection layer comprise the 0.005-99.95 weight portion based on carbon compound.
15, the Organnic electroluminescent device of claim 9, wherein based on the hole transmission layer of 100 weight portions, hole transmission layer comprise the 0.005-99.95 weight portion based on carbon compound.
16, a kind of Organnic electroluminescent device comprises:
Substrate;
Be formed on suprabasil first electrode;
Be formed on the hole transmission layer on first electrode;
Be formed on the emission layer on the hole transmission layer; With
Be formed on second electrode on the emission layer, wherein
The resilient coating that forms based on carbon compound is inserted between first electrode and the hole transmission layer.
17, the Organnic electroluminescent device of claim 16 also comprises the hole injection layer that is formed between first electrode and the resilient coating.
18, the Organnic electroluminescent device of claim 17, wherein based on the hole injection layer of 100 weight portions, hole injection layer comprise the 0.005-99.95 weight portion based on carbon compound.
19, the Organnic electroluminescent device of claim 16, wherein based on the hole transmission layer of 100 weight portions, hole transmission layer comprise the 0.005-99.95 weight portion based on carbon compound.
20, the Organnic electroluminescent device of claim 16 between the emission layer and second electrode, also comprises the one deck at least in hole blocking layer, electron injecting layer and the electron transfer layer.
21, the Organnic electroluminescent device of claim 16, wherein the thickness of resilient coating is 0.1-100nm.
22, a kind of Organnic electroluminescent device comprises:
Substrate;
Be formed on suprabasil first electrode;
Be formed on the hole injection layer on first electrode;
Be formed on the hole transmission layer on the hole injection layer;
Be formed on the emission layer on the hole transmission layer; With
Be formed on second electrode on the emission layer, wherein
Be inserted between hole injection layer and the hole transmission layer by the resilient coating that forms based on carbon compound.
23, the Organnic electroluminescent device of claim 22 wherein comprises at least a compound of the complex based on fullerene, carbon nano-tube, carbon fiber, carbon black, graphite, Cabbeen carbon, MgC60, CaC60 and the SrC60 that are selected from fullerene, contain metal based on carbon compound.
24, the Organnic electroluminescent device of claim 22, wherein the thickness of resilient coating is 0.1-100nm.
25, the Organnic electroluminescent device of claim 22, wherein based on the hole injection layer of 100 weight portions, hole injection layer comprise the 0.005-99.95 weight portion based on carbon compound.
26, the Organnic electroluminescent device of claim 22, wherein based on the hole transmission layer of 100 weight portions, hole transmission layer comprise the 0.005-99.95 weight portion based on carbon compound.
27, the Organnic electroluminescent device of claim 22 between the emission layer and second electrode, also comprises the one deck at least in hole blocking layer, electron injecting layer and the electron transfer layer.
28, a kind of Organnic electroluminescent device comprises:
Substrate;
Be formed on suprabasil first electrode;
Be formed on the emission layer on first electrode;
Be formed on the electron transfer layer on the emission layer; With
Be formed on second electrode on the electron transfer layer; Wherein electron transfer layer comprises electron transport material and based on carbon compound.
29, the Organnic electroluminescent device of claim 28 wherein comprises at least a compound of the complex based on fullerene, carbon nano-tube, carbon fiber, carbon black, graphite, Cabbeen carbon, MgC60, CaC60 and the SrC60 that are selected from fullerene, contain metal based on carbon compound.
30, the Organnic electroluminescent device of claim 28 wherein based on the electron transfer layer of 100 weight portions, is the 0.005-99.95 weight portion based on the content of carbon compound.
31, the Organnic electroluminescent device of claim 28 between first electrode and emission layer, also comprises the one deck at least that is selected from hole injection layer and the hole transmission layer.
32, the Organnic electroluminescent device of claim 31, also be included between first electrode and the hole injection layer, by the resilient coating that forms based on carbon compound.
33, the Organnic electroluminescent device of claim 28 also comprises the hole transmission layer that is inserted between first electrode and the emission layer, and be inserted between first electrode and the hole transmission layer, by the resilient coating that forms based on carbon compound.
34, the Organnic electroluminescent device of claim 31, also be included between hole injection layer and the hole transmission layer, by the resilient coating that forms based on carbon compound.
35, the Organnic electroluminescent device of claim 28 between the electron transfer layer and second electrode, also comprises the one deck at least in electron injecting layer and the hole blocking layer.
36, the Organnic electroluminescent device of claim 28, wherein the thickness of resilient coating is 0.1-100nm.
37, a kind of preparation comprises the method for the Organnic electroluminescent device that is inserted in the emission layer between first electrode and second electrode, its be included between the emission layer and first electrode form thickness be 0.1nm-100nm, by the resilient coating that forms based on carbon compound.
38, the method for claim 37, wherein resilient coating deposits with the deposition rate of 0.01nm/s-0.2nm/s.
39, the method for claim 38, wherein resilient coating deposits to the thickness of 1nm-5nm with the deposition rate of 0.01nm/s-0.05nm/s.
40, the method for claim 38, wherein resilient coating deposits to the thickness of 5nm-10nm with the deposition rate of 0.05nm/s-0.2nm/s.
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| KR1020040081114 | 2004-10-11 | ||
| KR1020040081114A KR100637178B1 (en) | 2004-10-11 | 2004-10-11 | Organic electroluminescence device |
| KR1020050071502 | 2005-08-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104576963A (en) * | 2014-12-18 | 2015-04-29 | 苏州汉克山姆照明科技有限公司 | Organic LED of multilayer structure |
| CN105789464A (en) * | 2014-12-22 | 2016-07-20 | 固安翌光科技有限公司 | Organic light-emitting device |
| CN113881284A (en) * | 2021-09-28 | 2022-01-04 | 惠科股份有限公司 | Nano graphite printing liquid, preparation method thereof and organic light-emitting diode |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100622229B1 (en) * | 2005-03-16 | 2006-09-14 | 삼성에스디아이 주식회사 | Luminescence display devices using the fullerene based carbon compounds and method for preparing the same |
| KR100787460B1 (en) * | 2006-09-21 | 2007-12-26 | 삼성에스디아이 주식회사 | Method for preparing organic luminescence device and organic luminescence device prepared by the method |
| KR101390022B1 (en) * | 2007-02-16 | 2014-04-29 | 삼성전자주식회사 | Nitrogen containing heteroaromatic ligand/transition metalcomplexes, buffer layer comprising the complexes and organic thin film transistor comprising the buffer layer |
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| KR102501666B1 (en) | 2016-01-11 | 2023-02-21 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104576963A (en) * | 2014-12-18 | 2015-04-29 | 苏州汉克山姆照明科技有限公司 | Organic LED of multilayer structure |
| CN105789464A (en) * | 2014-12-22 | 2016-07-20 | 固安翌光科技有限公司 | Organic light-emitting device |
| CN105789464B (en) * | 2014-12-22 | 2019-04-23 | 固安翌光科技有限公司 | Organic electroluminescence device |
| CN113881284A (en) * | 2021-09-28 | 2022-01-04 | 惠科股份有限公司 | Nano graphite printing liquid, preparation method thereof and organic light-emitting diode |
| CN113881284B (en) * | 2021-09-28 | 2022-08-02 | 惠科股份有限公司 | Nano graphite printing liquid, preparation method thereof and organic light-emitting diode |
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| KR100637178B1 (en) | 2006-10-20 |
| CN100557848C (en) | 2009-11-04 |
| KR20060032099A (en) | 2006-04-14 |
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