CN100495763C - Organic electroluminescence display of black electrode structure and its manufacturing method - Google Patents
Organic electroluminescence display of black electrode structure and its manufacturing method Download PDFInfo
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- CN100495763C CN100495763C CNB200610060571XA CN200610060571A CN100495763C CN 100495763 C CN100495763 C CN 100495763C CN B200610060571X A CNB200610060571X A CN B200610060571XA CN 200610060571 A CN200610060571 A CN 200610060571A CN 100495763 C CN100495763 C CN 100495763C
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Abstract
An organic electroluminescent display with black electrode structure is prepared as setting a luminous layer on organic film layer, utilizing cathode as black electrode formed by thin metal electrode reflection layer and organic material functional layer as well as thick metal electrode reflection layer, forming organic material functional layer by at least two types of organic materials being used to complement optical property to each other so as to decrease light reflectivity of visible light. The preparing method of black electrode is also disclosed.
Description
Technical field
The present invention relates to a kind of display of organic electroluminescence and preparation method thereof, relate in particular to display of organic electroluminescence of black electrode structure and preparation method thereof.
Background technology
Develop low driving voltage (＜10V first with practical value since the Deng Qingyun of Kodak company in 1987,1000cd/m2) since the OLED device (Alq3 is as luminescent layer), the OLED technology is practicability progressively, organic light emitting display is considered to planar luminescent display device of new generation, and Display Technique will face new revolution again.Because of it has active illuminating, plurality of advantages such as the contrast height can slimming, and response speed is fast is acknowledged as the main force of display of future generation.And, make that the contrast of OLED display screen is relatively poor because the luminance factor of aluminium and magnesium silver cathode electrode is higher, especially under outdoor environment, the OLED display screen display effect is poorer, is difficult to satisfy requirement of mass production.
Now, thereby the reflection that OLED display screen manufacturer mostly uses polaroid to reduce cathode electrode improves contrast, though it is ripe relatively to paste the polaroid technology, and it is effectively simple, but, polaroid has but increased the cost of manufacture of OLED display screen, make the power consumption of OLED display screen improve greatly, most importantly, the thickness of OLED display screen is increased about 0.3mm, these shortcomings are disagreed with current OLED display screen developing direction, have offset the low-power consumption of OLED display screen, advantage such as ultra-thin, will hinder the market development of OLED display screen.
In order to replace polaroid, mentioned the method for multiple making black electrode in document and the patent, for example U.S. Patent number 6,411, the black electrode of mentioning in 019, its structure is the conductive oxide functional layer of the growth of the method by sputter layer of transparent between skim metal electrode and reflective metals electrode, utilizes the absorption of light and the reflectivity that the destructive interference principle reduces electrode greatly.But sputtering method has very big negative effect to sheet metal electrode and electron transfer layer and electron injecting layer, the scale volume production that is unfavorable for the OLED device, therefore, mention the method evaporation organic material that uses evaporation in the document again and replace inorganic material, for example organic material of the use of mentioning among Applied Physics wall bulletin 83 (2003) 186-189 and the method that metal steams altogether.But the functional layer in the prior art between sheet metal electrode and the reflective metals electrode has only been used a kind of material of organic or inorganic, utilize the destructive interference principle of light to make black electrode, yet a kind of material also can not have extinction characteristic in whole visible spectrum, its refractive index is also fixed, so in the reflectivity of optimizing black electrode and reflectance spectrum chromaticity coordinates great limitation is arranged.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of organic electroluminescence display of black electrode structure and preparation method thereof, can obviously reduce the reflectivity of cathode electrode, the destruction that has brought when having avoided simultaneously using sputtering method deposition inorganic material to thin metal layer and organic layer.
The present invention adopts following technical scheme: a kind of organic electroluminescence display of black electrode structure comprises substrate, anode, negative electrode and the organic thin film layer between anode and negative electrode; Described organic thin film layer comprises one deck luminescent layer at least; Described negative electrode is a black electrode, promptly comprises one being positioned at thin metal electrode reflector on the organic thin film layer, placing the organic material functional layer on the thin metal electrode reflector and placing thick metal electrode reflector on the organic material functional layer; Wherein: described organic material functional layer comprises CuPc and Alq3 or CuPc and two kinds of organic materials of Rubrene, the completion mutually of the optical characteristics of these two kinds of organic materials, reducing the optical effect of light reflectance in the visible-range, and the proportioning between two kinds of organic materials is 10:90 to 90:10.
In the black electrode, the thickness in described thin metal electrode reflector is the 1-15 nanometer, and the thickness of described organic material functional layer is the 30-200 nanometer, and the thickness in described thick metal electrode reflector is greater than 80 nanometers.
Described organic thin film layer also comprises at the hole injection layer between anode and the luminescent layer and hole transmission layer and electron injecting layer between negative electrode and luminescent layer and electron transfer layer.
The manufacture method of organic electroluminescence display of black electrode structure of the present invention, this method comprises the steps:
A. anode purge substrate;
B. anode substrate preliminary treatment;
C. evaporation organic thin film layer on anode substrate;
D. making black electrode on the organic thin film layer: on organic thin film layer, make thin metal electrode reflector earlier, on thin metal electrode reflector, make organic material function layer again, on the organic material functional layer, make thick metal electrode reflector at last;
E. device package;
In described step D, the organic material functional layer adopts CuPc and Alq3 or CuPc and two kinds of common evaporations of organic material with optical characteristics completion of Rubrene to form, and the proportioning between two kinds of organic materials is 10:90 to 90:10.
In the step D that makes black electrode, the various materials of the material in described thin metal electrode reflector and the material in thick metal electrode reflector and composition organic material functional layer all adopt independently evaporation source, and use the constant rate of speed control mode to determine the thickness of each layer.
Among the described step C, the order of evaporation organic thin film layer is followed successively by: hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.
Compare with prior art, organic electroluminescence display of black electrode structure of the present invention uses two kinds or above organic material to make organic material function layer in black electrode, utilize the intrinsic property of organic material by optimization, be the sink effect of organic material to visible light, obviously reduce the reflectivity of cathode electrode, improved the contrast of OLED display screen; And luminous efficiency is about 60% of a commonplace components efficient, apparently higher than the OLED efficient of the subsides polaroid that uses the identity unit structure (have only commonplace components luminous efficiency about 40%); Compare with commonplace components, its chromaticity coordinates is close, does not influence the electroluminescence performance of OLED display screen; The destruction to thin metal layer and organic layer that has brought when manufacture method of the present invention has been avoided using sputtering method deposition inorganic material has avoided adopting metal and organic material to steam the cross pollution phenomenon of bringing altogether; In conjunction with advantages such as OLED display screen light weight, thin thickness, promoted the market competitiveness of OLED display screen again; In addition, the OLED display screen that uses this kind method to make can not increase the production burden of volume production line, can not prolong the OLED display screen productive temp time yet, and is good with the equipment collocation, can promote on the volume production line fully.
Description of drawings
Fig. 1 is the basic structure schematic diagram of organic electroluminescence display of black electrode structure spare of the present invention;
Fig. 2 is the structural representation of described black electrode negative electrode 3;
Fig. 3 is the reflectance spectrum curve chart of the embodiment of the invention one;
Fig. 4 is the reflectance spectrum curve chart of the embodiment of the invention two;
Fig. 5 is the reflectance spectrum curve comparison diagram of the embodiment of the invention three and ordinary electrode blue-light device.
Embodiment
Be described in further detail below in conjunction with the most preferred embodiment shown in the accompanying drawing.
The basic structure of organic electroluminescence display of black electrode structure of the present invention is followed successively by as shown in Figure 1 from the bottom to top: substrate 1, anode 2, organic thin film layer 4 and negative electrode 3.Wherein, described organic thin film layer 4 includes but not limited to from the bottom to top successively: hole injection layer 42, hole transmission layer 43, luminescent layer 41, electron transfer layer 45 and electron injecting layer 44.As shown in Figure 2, described negative electrode 3 is a black electrode structure, comprises successively from the bottom to top: thickness the thin metal electrode reflector 31 between the 1-15 nanometer, thickness between the 30-200 nanometer organic material functional layer 32 and thickness greater than the thick metal electrode reflector 33 of 80 nanometers.Described anode 2 is transparent or semitransparent electrode, can adopt indium tin oxide (ITO) or indium-zinc oxide inorganic material such as (IZO) or semi-transparent metals film, macromolecule organic membrane etc.; The material of described luminescent layer 41 can adopt fluorescent material or phosphor material, can send redness, green, blueness or white light; Materials such as aluminium, magnesium silver alloy, calcium or barium can be adopted in described thin metal electrode reflector 31 and thick metal electrode reflector 33.
The special feature of display of the present invention is: the organic material functional layer 32 of described black electrode comprises at least two kinds of organic materials, the completion mutually of the optical characteristics of this two or more organic material, make that thus this organic material functional layer 32 also can extinction at whole visible spectrum, add the destructive interference principle of light, can obtain to reduce the optical effect of light reflectance in the visible-range, the black electrode chromaticity coordinates more can point (0.33,0.33) near waiting of atmospheric reflectance spectral chromaticity coordinate.The organic material of described composition organic material functional layer 32 can adopt but be not limited to CuPc (CuPc), NPB (N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-diphenyl-4,4 '-diamines), the derivative of Alq3 (oxine aluminium), Rubrene (rubrene) or above-mentioned material etc.Provide several embodiment of black electrode structure below:
It is the aluminum material of 3 nanometers that thickness is adopted in embodiment one, described thin metal electrode reflector 31, described organic material functional layer 32 is selected CuPc that inhales ruddiness and the Alq3 that inhales the UV-blue light for use, its thickness is 70 nanometers, the proportioning of two kinds of materials is 1:1, and Fig. 3 is the reflectance spectrum curve chart of the blue-light device of employing the foregoing description.
It is the aluminum material of 3.5 nanometers that thickness is adopted in embodiment two, described thin metal electrode reflector 31, described organic material functional layer 32 is selected CuPc and Rubrene for use, its thickness is 70 nanometers, the proportioning of two kinds of materials is 1:1, and Fig. 4 is the reflectance spectrum curve chart of the blue-light device of employing the foregoing description.
Embodiment three, it is the aluminum material of 4 nanometers that thickness is adopted in described thin metal electrode reflector 31, described organic material functional layer 32 is selected CuPc and Rubrene for use, its thickness is 90 nanometers, the proportioning of having listed above-mentioned two kinds of materials among Fig. 5 is respectively 90:0, the reflectance spectrum curve chart of blue-light device when 80:10 and 70:20, as seen the content as Rubrene increases gradually, reflectivity in the shortwave strong point reduces gradually, and the reflectivity that black electrode is mixed the device that adopts above-mentioned two kinds of materials is starkly lower than commonplace components, also is lower than the simple device (during CuPc:Rubrene=90:0) that adopts a kind of material of black electrode.
Organic electroluminescence display of black electrode structure of the present invention is to adopt high vacuum coating equipment, makes by the mode of vacuum evaporation, and its entire making process all is all disposable under the situation of not destroying vacuum to finish following institute in steps:
A. anode purge substrate;
B. anode substrate preliminary treatment;
C. evaporation organic thin film layer 4 on anode substrate, its evaporation is followed successively by in proper order: hole injection layer 42, hole transmission layer 43, luminescent layer 41, electron transfer layer 45 and electron injecting layer 44;
D. evaporation black electrode on organic thin film layer 4, its evaporation is followed successively by in proper order: thin metal electrode reflector 31, organic material functional layer 32 and thick metal electrode reflector 33, wherein, 32 two kinds of employings of organic material functional layer or the above common evaporation of the different organic materials with optical characteristics completion form, metal electrode 31 and 33 material and the two or more material of organic material functional layer 32 all have independently evaporation source, and use the constant rate of speed control mode to determine the thickness of each layer;
E. device package.
Claims (6)
1, a kind of organic electroluminescence display of black electrode structure, comprise substrate (1), anode (2), negative electrode (3) and be positioned at anode (2) and negative electrode (3) between organic thin film layer (4); Described organic thin film layer (4) comprises one deck luminescent layer (41) at least; Described negative electrode (3) is a black electrode, promptly comprises one being positioned at thin metal electrode reflector (31) on the organic thin film layer (4), placing the organic material functional layer (32) on the thin metal electrode reflector (31) and placing thick metal electrode reflector (33) on the organic material functional layer (32); It is characterized in that: described organic material functional layer (32) comprises CuPc and Alq3 or CuPc and two kinds of organic materials of Rubrene, the completion mutually of the optical characteristics of these two kinds of organic materials, reducing the optical effect of light reflectance in the visible-range, and the proportioning between two kinds of organic materials is 10:90 to 90:10.
2, organic electroluminescence display of black electrode structure according to claim 1, it is characterized in that: in the black electrode, the thickness in described thin metal electrode reflector (31) is the 1-15 nanometer, the thickness of described organic material functional layer (32) is the 30-200 nanometer, and the thickness in described thick metal electrode reflector (33) is greater than 80 nanometers.
3, organic electroluminescence display of black electrode structure according to claim 1 and 2 is characterized in that: described organic thin film layer (4) also comprise hole injection layer (42) and the hole transmission layer (43) that is positioned between anode (2) and the luminescent layer (41) and be positioned at negative electrode (3) and luminescent layer (41) between electron injecting layer (44) and electron transfer layer (45).
4, a kind of manufacture method of organic electroluminescence display of black electrode structure, this method comprises the steps:
A. anode purge substrate;
B. anode substrate preliminary treatment;
C. evaporation organic thin film layer (4) on anode substrate;
D. go up at organic thin film layer (4) and make black electrode: go up at organic thin film layer (4) earlier and make thin metal electrode reflector (31), go up in thin metal electrode reflector (31) again and make organic material function layer (32), go up in organic material functional layer (32) at last and make thick metal electrode reflector (33);
E. device package;
It is characterized in that: among the described step D, organic material functional layer (32) adopts CuPc and Alq3 or CuPc and two kinds of common evaporations of organic material with optical characteristics completion of Rubrene to form, and the proportioning between two kinds of organic materials is 10:90 to 90:10.
5, the manufacture method of organic electroluminescence display of black electrode structure according to claim 4, it is characterized in that: in the step D that makes black electrode, the various materials of the material in the material in described thin metal electrode reflector (31) and thick metal electrode reflector (33) and composition organic material functional layer (32) all adopt independently evaporation source, and use the constant rate of speed control mode to determine the thickness of each layer.
6, the manufacture method of organic electroluminescence display of black electrode structure according to claim 4, it is characterized in that: among the described step C, the order of evaporation organic thin film layer (4) is followed successively by: hole injection layer (42), hole transmission layer (43), luminescent layer (41), electron transfer layer (45) and electron injecting layer (44).
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