CN100448059C - Colour stable organic-inorganic heterogeneous white electroluminescent device and preparing method - Google Patents
Colour stable organic-inorganic heterogeneous white electroluminescent device and preparing method Download PDFInfo
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- CN100448059C CN100448059C CNB2006100026350A CN200610002635A CN100448059C CN 100448059 C CN100448059 C CN 100448059C CN B2006100026350 A CNB2006100026350 A CN B2006100026350A CN 200610002635 A CN200610002635 A CN 200610002635A CN 100448059 C CN100448059 C CN 100448059C
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Abstract
The present invention relates to an organic-inorganic heterojunction white electroluminescent device with stable colors and a preparation method thereof. Firstly, ITO glass is washed; secondly, an organic cavity transmission layer material concurrently used as a luminous layer material is coated on the ITO glass substrate by film shake and other methods; a thin inorganic layer is formed on the organic cavity transmission layer concurrently used as the luminous layer through vapor deposition by electron beam evaporation and other methods; then thermal evaporation and other methods are used for the vapor deposition of an organic electron transmission layer concurrently used as a luminous layer; finally, a back electrode is formed by vapor deposition, and an electroluminescent device is prepared. By utilizing the characteristic of an energy band structure of an inorganic material, and by utilizing large carrier mobility, organic material layers at both sides of a thin inorganic material layer can simultaneously emit light. By utilizing a certain absorption and permeation function of the thin inorganic layer, and by utilizing a color complementary principle, light coming out of the transparent electrode can be white light. The present invention overcomes the defect that the color of light which is emitted by a device is changed when voltage is increased. By optimizing the structure of a device, a white electroluminescent device with good color rendering and a stable color can be obtained.
Description
Technical field
The present invention relates to organic-inorganic heterogeneous white electroluminescent device of a kind of colour stable and preparation method thereof.Be a kind ofly to embed inorganic II-VI compounds of group thin layer at the organic heterojunction interface and obtain white electroluminescence device of colour stable and preparation method thereof specifically.
Background technology
Usually, in the electroluminescent device of bilayer and sandwich construction, because the influence of device inside heterojunction boundary place interface potential barrier, the charge carrier of this place, interface accumulation can increase along with the alive increase of institute, the electric field of each organic layer of device inside can redistribute, and the voltage that is correspondingly changing on each layer of device distributes and the position of light-emitting zone in each layer, and then changes the shape of spectrum, influences glow color.Especially, if the interaction of electron transfer layer in the double-deck organic electroluminescence device and hole transmission layer is stronger, then the luminous of exciplex (Exciplex or Electroplex) can appear in this heterojunction boundary place.If utilize the high and relative more stable characteristics of charge carrier (comprising electronics and the hole) mobility of inorganic material, embed one deck thin layer of inorganic material at the interface at organic heterojunction, can realize the luminous of thin layer of inorganic material both sides organic material.Utilize the complementary colours principle, when both sides organic material luminous can be mixed into white light mutually, then can obtain the good white luminous device of color rendering.Change the added voltage of device and just change luminous intensity, the glow color of device will be constant substantially.
Summary of the invention
Purpose of the present invention just provides organic-inorganic heterogeneous white electroluminescent device of a kind of colour stable and preparation method thereof, using this invention can overcome the organic heterojunction interface, exciplex may to occur luminous and reduce luminous efficiency, can solve the glow color of device again with problems such as voltage change.
The present invention is achieved in that
White electroluminescence device structure of the present invention is:
On glass substrate, be coated with one deck ito anode, on ito anode, be coated with one deck organic cavity transmission layer luminescent layer and one deck organic electron transport layer luminescent layer of holding concurrently of holding concurrently; Between this two-layer organic layer, one deck thin layer of inorganic material is arranged; On holding concurrently luminescent layer, organic electron transport layer is coated with metal back electrode.
Organic-inorganic heterogeneous white electroluminescent device preparation method of the present invention is as follows:
(1) cleans the glass substrate that is coated with one deck ito anode; In addition, the hold concurrently solution of luminescent layer material of preparation organic cavity transmission layer;
(2) organic cavity transmission layer the is held concurrently solution of luminescent layer material is coated on the cleaned glass substrate that is coated with one deck ito anode by the method for getting rid of film and oven dry;
(3) utilize on the method for electron beam evaporation holds concurrently luminescent layer with the inorganic material evaporation to organic cavity transmission layer, underlayer temperature is suitable;
(4) after cooling, again on inorganic thin film layer with the way evaporation organic electron transport layer of the thermal evaporation luminescent layer material of holding concurrently;
(5) evaporation back electrode material.
The present invention compares with the luminous method that obtains white electroluminescence of organic heterojunction exciplex at the interface of present use, its advantage is: at first, it is luminous and reduce luminous efficiency that the introducing of II-VI family inorganic material can effectively avoid the organic heterojunction interface to form exciplex; Secondly, electron transfer layer holds concurrently luminescent layer and the component of wherein mixing (as dyestuff etc.) can be optimized, the color of device can further be optimized, and in case determined hold concurrently luminescent layer and wherein after each doping component of organic electron transport layer, the color of device is basic definite, no longer changes along with the change of voltage; Once more, because the characteristics of the band structure of used inorganic material (II-VI compounds of group) itself, making does not have potential barrier from the electron transfer layer luminescent layer injected electrons of holding concurrently at the interface at this organic/inorganic, and at this organic/inorganic certain hole injection barrier is arranged at the interface from the hole transmission layer luminescent layer injected holes of holding concurrently, injection that can equilibrium carrier makes the organic layer of inorganic material layer both sides all have luminous; In addition, the inorganic material film that is inserted itself all has certain transmitance to different wavelength.Be understood that, electron mobility that inorganic material is higher and hole mobility make charge carrier can penetrate inorganic layer smoothly and arrive in the corresponding organic layer and to form exciton and recombination luminescence, and the thickness by each layer of optimised devices can obtain that color rendering is good, the white luminous device of colour stable again.Owing to used the stronger inorganic material of chemical stability, so the stability of device has strengthened.
Description of drawings
Fig. 1 is a white electroluminescence device structure chart of the present invention.
Fig. 2 is preparation method's block diagram of white electroluminescence device.
Fig. 3 is under different voltages, device ITO/PVK (50nm)/ZnSe (80nm)/Alq
3: DCJTB (0.5wt.%) (10nm)/electroluminescent spectrum of Al.
Fig. 4 is organic-inorganic heterogeneous device ITO/PVK/ZnSe/Alq
3The level structure figure of/Al.
Embodiment
The specific embodiment of the present invention as shown in Figure 1, 2, its step is as follows:
(1) cleans the glass substrate that is coated with one deck ito anode; (concentration can select 5～15mg/ml) to the chloroformic solution of preparation organic hole transferring material PVK.Present embodiment can be selected any one among 5mg/ml, 10mg/ml and the 15mg/ml.
(2) PVK solution is coated on the cleaned ito anode that is plated on the glass substrate by the method for getting rid of film, thickness is 50nm, and oven dry is with standby; (note: for can not be with the material (as the material of blue light-emittings such as TPD and NPB) of the mode film forming of getting rid of film, can be by the way film forming of evaporation)
(3) on the method for deposited by electron beam evaporation was held concurrently luminescent layer with inorganic material (as the II-VI compounds of group ZnSe of broad stopband and ZnO etc.) evaporation to organic cavity transmission layer, underlayer temperature can be selected 100 ℃, and thickness is 80nm; (for other material, also available other film plating process (as MBE etc.))
(4) after cooling, again on inorganic thin film layer with the method evaporation organic electron transport layer of the thermal evaporation luminescent layer materials A lq that holds concurrently
3(being mixed with the DCJTB dyestuff of 0.5wt.%), the about 10nm of thickness;
(5) evaporation back electrode materials A l electrode.
According to above method, we have obtained following electroluminescent device:
ITO/PVK(50nm)/ZnSe(80nm)/Alq
3:DCJTB(0.5wt.％)(10nm)/Al。Be coated with on its surface on the glass substrate 1 of ito anode 2, one deck organic cavity transmission layer luminescent layer 3 and one deck organic electron transport layer luminescent layer 5 of holding concurrently of holding concurrently is arranged, between these two inorganic layers, one deck thin layer of inorganic material 4 is arranged, on holding concurrently luminescent layer 5, organic electron transport layer is coated with metal back electrode 6.Electroluminescent spectrum as shown in Figure 3, under 15V voltage, we have obtained the white light of chromaticity coordinates (CIE) for (0.32,0.38), along with increasing of voltage, the device working stability, color is also very stable.It should be noted that and to pass through optimised devices thickness, particularly pay close attention to (2), (3), (4) step, optimize suitable device architecture, can make that color rendering is good, the white electroluminescence device of colour stable.
Claims (5)
1. the organic-inorganic heterogeneous white electroluminescent device of a colour stable is characterized in that: be coated with one deck ito anode and one deck organic cavity transmission layer luminescent layer and one deck organic electron transport layer luminescent layer of holding concurrently of holding concurrently on glass substrate; Between this two-layer organic layer, one deck thin layer of inorganic material is arranged; On holding concurrently luminescent layer, organic electron transport layer is coated with metal back electrode.
2. the organic-inorganic heterogeneous white electroluminescent device of colour stable according to claim 1 is characterized in that the hole transmission layer luminescent layer of holding concurrently is hole transmission layer and organic luminous layer by further hierarchy optimization; Simultaneously, the electron transfer layer luminescent layer of holding concurrently is electron transfer layer and organic luminous layer by further hierarchy optimization, like this, further reduces the bright voltage that rises of device.
3. the preparation method of the organic-inorganic heterogeneous white electroluminescent device of a colour stable is characterized in that its preparation method is as follows:
(1) cleans the glass substrate that is coated with one deck ito anode; The hold concurrently solution of luminescent layer material of preparation organic hole transferring material;
(2) organic cavity transmission layer the is held concurrently solution of luminescent layer material is coated on the cleaned glass substrate that is coated with one deck ito anode by the method for getting rid of film and oven dry;
(3) on the method for utilizing electron beam evaporation is held concurrently luminescent layer with the inorganic material evaporation to the suitable organic cavity transmission layer of temperature;
(4) after cooling, again on inorganic thin film layer with the method evaporation organic electron transport layer of the thermal evaporation luminescent layer material of holding concurrently;
(5) evaporation back electrode material on organic electron transport layer is held concurrently the luminescent layer material at last.
4. the preparation method of the organic-inorganic heterogeneous white electroluminescent device of colour stable according to claim 3 is characterized in that in the step (2), for can not be with the material of the blue light-emitting that gets rid of the film method film forming, by the method film forming of evaporation.
5. the preparation method of the organic-inorganic heterogeneous white electroluminescent device of colour stable according to claim 3, it is characterized in that in step (3), for the inorganic material that can not utilize the electron beam evaporation film forming, come film forming with the method for thermal evaporation or MBE.
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| CNB2006100026350A CN100448059C (en) | 2006-01-26 | 2006-01-26 | Colour stable organic-inorganic heterogeneous white electroluminescent device and preparing method |
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| CNB2006100026350A CN100448059C (en) | 2006-01-26 | 2006-01-26 | Colour stable organic-inorganic heterogeneous white electroluminescent device and preparing method |
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| CN100448059C true CN100448059C (en) | 2008-12-31 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294834A (en) * | 1999-02-15 | 2001-05-09 | 出光兴产株式会社 | Organic electroluminescent element and method for manufacturing the same |
| US20040166327A1 (en) * | 2003-02-20 | 2004-08-26 | Makoto Utsumi | Color conversion filter substrate, color conversion type multicolor display having the same, and method of manufacturing the same |
| CN1612661A (en) * | 2003-10-29 | 2005-05-04 | 三星Sdi株式会社 | Electroluminescent device using metal nano-particles |
| JP2005317450A (en) * | 2004-04-30 | 2005-11-10 | Tdk Corp | Organic el element |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294834A (en) * | 1999-02-15 | 2001-05-09 | 出光兴产株式会社 | Organic electroluminescent element and method for manufacturing the same |
| US20040166327A1 (en) * | 2003-02-20 | 2004-08-26 | Makoto Utsumi | Color conversion filter substrate, color conversion type multicolor display having the same, and method of manufacturing the same |
| CN1612661A (en) * | 2003-10-29 | 2005-05-04 | 三星Sdi株式会社 | Electroluminescent device using metal nano-particles |
| JP2005317450A (en) * | 2004-04-30 | 2005-11-10 | Tdk Corp | Organic el element |
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