CN107170905B - A kind of highly reliable passive organic electroluminescent device and preparation method thereof - Google Patents
A kind of highly reliable passive organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN107170905B CN107170905B CN201710544247.3A CN201710544247A CN107170905B CN 107170905 B CN107170905 B CN 107170905B CN 201710544247 A CN201710544247 A CN 201710544247A CN 107170905 B CN107170905 B CN 107170905B
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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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
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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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/17—Passive-matrix OLED displays
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Abstract
The invention belongs to organic electroluminescence device technical fields, and in particular to a kind of highly reliable passive organic electroluminescent device.Highly reliable passive organic electroluminescent device of the present invention, on the basis of existing structure device, the current-limiting layer formed by introducing selected material, to limit the current value by specific pixel, simultaneously further through corresponding second plate layer being arranged on the current-limiting layer to realize the matching of work function, on the one hand increase electric current injection, while reducing the voltage because of caused by interfactial work Functions mismatch and rising, can effectively avoid the unsteady phenomenas such as screen body drain electricity.
Description
Technical field
The invention belongs to organic electroluminescence device technical fields, and in particular to a kind of highly reliable passive organic electroluminescent
Device.
Background technique
OLED (Organic Light Emitting Display, organic light emitting display) refers to organic semiconducting materials
With luminescent material under electric field driven, the phenomenon that injection by carrier with composite guide photoluminescence.Its typical organic electroluminescence hair
Optical device structure includes that the first electrode and second of the anode and the cathode as electron injection that are used as hole injection is arranged in
Organic electroluminescent media between electrode.Its principle is to use ito transparent electrode and metal electrode respectively as the anode of device
And cathode, under certain voltage driving, electrons and holes are injected into electron and hole transport layer, electronics from cathode and anode respectively
Pass through electron and hole transport layer respectively with hole and move to luminescent layer, and meet in luminescent layer, form exciton and makes to shine
Molecule excitation, the latter issue visible light by radiative relaxation.Radiant light can be from ITO unilateral observation to metal electrode film is simultaneously
Also play the effect in reflecting layer.Display is made and is referred to as organic light emitting display according to this principle of luminosity, is also OLED
Display.
Passive drive display of organic electroluminescence (PMOLED) is one kind of OLED device, typical PM-OLED by
Glass substrate, ito anode, organic luminous layer and cathode etc. are formed, wherein thin and transparent ito anode and metallic cathode is such as
With as sandwich organic luminous layer is sandwiched wherein, when the electronics that the hole of voltage injection anode and cathode come is in organic light emission
When layer combines, excites organic material and shine.Typical PMOLED device is driven by row (or column) scanning mode
(PMOLED screen circuit diagram is shown in Fig. 1), such as: a PMOLED dot matrix screen has M to arrange (anode), N row (cathode), the then resolution shielded
Rate is M*N.Cathode area staggered with anode is the light emitting region (can be considered as light emitting diode) of OLED, only when there is electricity
Circulate it is out-of-date can just shine, moment brightness is directly proportional with horizontal scanning line, such as show picture average brightness be 100cd/m2, have
96 horizontal scanning lines, then pixel display brightness must be greater than 9600cd/m2, while being also contemplated that caused by aperture opening ratio and light polarizing film
Loss, pixel intensity require generally at (2-4) × 104cd/m2Between.
As shown in Fig. 2, conventional PMOLED substrate, using Metal/ITO structure, wherein metal generally use Ag,
MoAlMo, Cr etc..Dot structure is general as shown, for example, longitudinal is ito anode, and lateral is Al metallic cathode.Usually this sets
For meter in driving, cathode connects cathode together, such as the first row cathode is chosen to connect.The column electrode of corresponding the first row, according to figure
Information exports corresponding current.It is equivalent to electric current to flow into from 12 road anodes, be flowed out from cathode all the way.So the resistivity meeting of cathode
Have a significant impact to screen body, usually setting counter electrode lead, to reduce surface resistance.
The characteristics of PMOLED device is that display pixel single-point brightness is very high, and opposite makes driving current density very
Greatly.Under high current density driving, some potential defects are easy to cause to run down via the driving of high current, and then cause
Shield body failure.
As shown in the defect enlarged drawing provided in Fig. 3 (100um × 100um), conventional PMOLED device is easy to appearance
Defect is small dim spot or bright spot of the size in 1um or so.Usual this defect is caused just since particle is in anode surface
Cathode locally causes (as shown in Figure 4) with the presence of leakage current.And under high current density or high-temperature work environment, this defect causes
Leakage current, can run down, and then cause entire pixel, or even a line (or column) of screen body fails.
In some organic electroluminescence devices (OLED) design, as disclosed one kind in Chinese patent CN101960639A
The scheme to be solved the above problems using short reduction layer proposed using mixed oxide as preventing defect layer, can be
The drawbacks described above of PMOLED device is solved the problems, such as to a certain extent.But the main purpose of the short reduction layer designed in above scheme
It is to increase resistance, it is therefore desirable to adjust suitable resistivity, while increased short reduction layer has since it is desired that with there is base
Match and have to meet appropriate work function, this has biggish difficulty in selection;Meanwhile above-mentioned design spininess to AMOLED and shines
Bright to be designed, the PMOLED device pixel under particular job electric current passes through the big problem of current density, and the structure of this method is set
Meter is then inconsiderate, influences application effect to a certain extent.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in a kind of highly reliable passive organic electroluminescent device is provided,
To solve the problems, such as passive organic electroluminescent device screen volume defect in the prior art.
In order to solve the above technical problems, a kind of highly reliable passive organic electroluminescent device of the present invention, including base
Plate, and form anode layer, organic function layer and cathode layer on the substrate, the device further include current-limiting layer with
And the material layer to match with the organic function layer work function.
Preferably, in the highly reliable passive organic electroluminescent device:
The anode layer successively includes first anode layer, current-limiting layer and the second sun along the close orientation substrate
Pole layer;Alternatively,
The cathode layer successively includes the first cathode layer, current-limiting layer and the second yin along the separate orientation substrate
Pole layer;
The second plate layer and second cathode layer are the material layer to match with the organic function layer work function.
The resistivity of the current-limiting layer is 1.0 × 101-1.0×103Ω/□。
Preferably, the resistivity of the current-limiting layer is 5.0 × 101-1.0×102Ω/□。
The material for forming the current-limiting layer includes metal oxide, organic polymer, small organic molecule, nano material
Or the composite material of above-mentioned material composition.
The material for forming the current-limiting layer includes mixed-metal oxides, metal oxide and polymer material it is mixed
Close the mixture of object or nano material and polymer material.
Preferably, the mixed-metal oxides are the mixture of zinc oxide and silica, can be adjusted by adjusting ratio
Whole resistivity;The metal oxide and polymer material are mixed into the mixtures such as tin indium oxide, ppv, resin;Nano material with
Polymer material mixture is nano silver and resinous material mixture.
Surface resistance<20 Ω/ of the first anode layer, the material for forming the second plate layer is work function>4.5eV
Metal oxide, metal or organic polymer material (surface resistance can be between 5-5000 Ω/).
The second plate layer is consistent with the figure of the first anode layer.
The anode layer and the organic luminous layer of the cathode layer intersection region form screen body light emitting pixel, second sun
The light emitting pixel structure of pole layer is divided into several subpixel areas less than visual range according to its concrete application field.
The area of each subpixel area is between (10-5000) μ m (10-5000) um.
Each subpixel area it is independent of each other include hexagonal structure, triangular structure of right angle, square structure or
Irregular graphic structure.
Each subpixel area, which is averaged, to be divided and in regularly arranged.
The material for forming first cathode layer is low-work-function material, such as Al, Ag, Mg work function are lower and are easy to electricity
The material of sub- transport layer collocation;The material for forming second cathode layer is surface resistance < 20 Ω/ conductive material.
The device is top illuminating device or bottom luminescent device.
The organic function layer includes hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer.
The invention also discloses a kind of method for preparing the highly reliable passive organic electroluminescent device, including it is as follows
Step:
(1) the selected substrate is made according to prior art conventional method, and forms selected first anode layer;
(2) current limit of selected material is prepared in the first anode layer surface according to prior art conventional method
Layer;
(3) the second plate layer is prepared in the current limit layer surface according to prior art conventional method, and ensured
The first anode layer is consistent with the figure of the second plate layer;
(4) organic function layer and the cathode layer is conventionally made, and encapsulates the preparation for completing screen body;Or
Person,
(1) the selected substrate is made according to prior art conventional method, and forms selected anode layer;
(2) organic function layer is conventionally made, and shows to form described second in the organic function layer
Cathode layer;
(3) current limit of selected material is prepared in the second cathode layer surface according to prior art conventional method
Layer;
(4) first cathode layer is prepared in the current limit layer surface according to prior art conventional method, and encapsulated
Complete the preparation of screen body;Alternatively,
(1) the selected substrate is made according to prior art conventional method, and forms selected cathode layer;
(2) organic function layer is conventionally made, and shows to form described second in the organic function layer
Anode layer;
(3) current limit of selected material is prepared in the second plate layer surface according to prior art conventional method
Layer, and ensure that the first anode layer is consistent with the figure of the second plate layer;
(4) first anode layer is prepared in the current limit layer surface according to prior art conventional method, and encapsulated
Complete the preparation of screen body;Alternatively,
(1) the selected substrate is made according to prior art conventional method, and forms selected first cathode layer;
(2) current limit of selected material is prepared in the first cathode layer surface according to prior art conventional method
Layer;
(3) second cathode layer is prepared in the current limit layer surface according to prior art conventional method;
(4) organic function layer and the anode layer is conventionally made, and encapsulates the preparation for completing screen body.
The method also includes the structures and arrangement mode according to the selected subpixel area, to the second plate
The step of layer is split.
The method also includes be conventionally made the hole injection layer, hole transmission layer, electron transfer layer and/
Or the step of electron injecting layer.
Highly reliable passive organic electroluminescent device of the present invention is selected on the basis of existing structure device by introducing
The current-limiting layer of material formation is determined, to limit the current value by specific pixel, while further through in the current-limiting layer
It is upper that corresponding second plate layer is set to realize the matching of work function, on the one hand increase electric current injection, while reducing because of interfactial work
Voltage caused by Functions mismatch rises, and can effectively avoid the unsteady phenomenas such as screen body drain electricity.On this basis, institute of the present invention
Device is stated further through for the specific operating brightness of PMOLED and operating current, the resistance setting of the current-limiting layer is done
Detailed design optimization, to ensure to ensure that the operating voltage and efficiency of screen body while reducing defect.
Highly reliable passive organic electroluminescent device of the present invention by carrying out piecemeal to anode pixels, and designs string
Join resistance, control reduces the generation of defect with this by the leakage current of single latent defect point;And by a certain electrode (example
If metal auxiliary electrode is arranged in anode ITO), lead resistance, reduction of fractions to a common denominator area in parallel light emitting sub-pixel are reduced;Pass through predetermined partition ruler
It is very little, it controls within the visual scale of people's vision, so that while ensuring to shield body stability, and will not be to the external sight of screen and vision
Effect has an impact.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is PMOLED screen circuit display figure;
Fig. 2 is PMOLED screen causes of defects schematic diagram;
Fig. 3 is PMOLED screen defect enlarged drawing;
Fig. 4 is the anode and cathode structure of conventional PMOLED;
Fig. 5 is dot structure schematic diagram in embodiment 2;
Fig. 6 is dot structure schematic diagram in embodiment 5.
Specific embodiment
Embodiment 1
The present embodiment chooses one 128 × 64 dot matrix screens, wherein 128 are classified as anode, 64 behavior cathodes.It is described highly reliable passive
Organic electroluminescence device, including substrate, and sequentially form anode layer, hole injection layer, hole biography on the substrate
Defeated layer, organic luminous layer, electron transfer layer and cathode layer, the anode layer successively include the first sun along the close orientation substrate
Pole layer, current-limiting layer and second plate layer.
The first anode use 150nm thickness ITO, current-limiting layer by PMMA, doping photosensitizer (t- butyl benzoic acid),
Blended metal oxide material (zinc oxide), dispersing agent are formed, and resistivity is 250 Ω/.The second plate layer is and has
Machine hole transmission layer matches good transparent conductive material.ITO layer thickness 2nm, mainly plays anode modification, improve anode to
The effect in organic hole implanted layer injection hole.
Highly reliable passive organic electroluminescent device described in the present embodiment, is prepared as follows:
Select ITO/MoAlMo substrate, by gluing, exposure, development, etching method, prepare respectively MoAlMo figure and
ITO pattern (conventional structure as shown in Figure 2);
Current-limiting layer is prepared on the surface ITO by existing conventional coating, exposure, developing method;
On aforesaid substrate surface, sputtering 2nm thick ito layer is coincide as second plate, figure and the first anode;
By way of vacuum evaporation, hole injection layer (m-MTDATA adulterates 2%F4tcnq), sky are prepared in aforesaid substrate
Cave transport layer (NPB), organic luminous layer (Alq3: C545T), electron transfer layer (Alq3), electron injecting layer (LiF), cathode (Al)
Deng, and encapsulate.
Embodiment 2
The present embodiment chooses one 128 × 64 dot matrix screens, wherein 128 are classified as anode, 64 behavior cathodes.It is described highly reliable passive
Organic electroluminescence device, including substrate, and sequentially form anode layer, hole injection layer, hole biography on the substrate
Defeated layer, organic luminous layer, electron transfer layer and cathode layer, the anode layer successively include the first sun along the close orientation substrate
Pole layer, current-limiting layer and second plate layer.Organic material and electron injection material, cathode selection is the same as embodiment 1.
The first anode use 150nm thickness ITO, current-limiting layer by PMMA, doping photosensitizer (t- butyl benzoic acid),
Blended metal oxide (zinc oxide) material, dispersing agent to be formed, and resistivity is 250 Ω/.The second plate layer is
Good transparent conductive material is matched with organic cavity transmission layer.ITO layer thickness 10nm, surface resistance < 500 Ω/, mainly
Anode modification is played, effect of the anode to organic hole implanted layer injection hole is improved.
Highly reliable passive organic electroluminescent device described in the present embodiment, is prepared as follows:
Select ITO/MoAlMo substrate, by gluing, exposure, development, etching method, prepare respectively MoAlMo figure and
ITO pattern (existing structure as shown in Figure 2);
Current-limiting layer is prepared on the surface ITO by existing conventional coating, exposure, developing method;
On aforesaid substrate surface, sputtering 10nm thick ito layer is as second plate, by gluing, exposure, developing process, second
Anode ITO layer is split as unit pixel in 10 × 10um2Zonule (dot structure as shown in Figure 5);
By way of conventional vacuum evaporation, hole injection layer, hole transmission layer, organic light emission are prepared in aforesaid substrate
Layer, electron transfer layer, electron injecting layer, cathode (Al) etc., and encapsulate.The choosing of organic material and electron injection material, cathode
Material is the same as embodiment 1.
Embodiment 3
The present embodiment chooses one 128 × 64 dot matrix screens, wherein 128 are classified as anode, 64 behavior cathodes.It is described highly reliable passive
Organic electroluminescence device, including substrate, and sequentially form anode layer, hole injection layer, hole biography on the substrate
Defeated layer, organic luminous layer, electron transfer layer and cathode layer, the anode layer successively include the first sun along the close orientation substrate
Pole layer, current-limiting layer and second plate layer.
The first anode uses 150nm thickness ITO, and by metal oxide materials, (tin indium oxide adulterates current-limiting layer
30% silica, 40% aluminium oxide) it is formed, by adjusting ratio, controlling its resistivity is 300 Ω/.
The second plate layer is that good oxidation film transparent conductive material is matched with organic cavity transmission layer.Oxidized metal
Molybdenum layer thickness 50nm mainly plays anode modification, improves effect of the anode to organic hole implanted layer injection hole.
Highly reliable passive organic electroluminescent device described in the present embodiment, is prepared as follows:
Select ITO/MoAlMo substrate, by gluing, exposure, development, etching method, prepare respectively MoAlMo figure and
ITO pattern (such as Fig. 2);
Current-limiting layer is prepared on the surface ITO by known sputtering, exposure, developing method;
On aforesaid substrate surface, sputtering 50nm molybdenum oxide layer is made as second plate by gluing, exposure, developing process
It is similar to first anode figure;
By way of vacuum evaporation, hole injection layer, hole transmission layer, organic luminous layer, electricity are prepared in aforesaid substrate
Sub- transport layer, electron injecting layer, cathode (Al) etc., and encapsulate.The selection of organic material and electron injection material, cathode is the same as real
Apply example 1.
Embodiment 4
The structure of highly reliable passive organic electroluminescent device described in the present embodiment is same as Example 1, and difference only exists
In, by cathode design be the first cathode (such as aluminium), current-limiting layer tungsten oxide, the second cathode layer aluminium, remaining technique with it is upper similar.
The selection of organic material and electron injection material, cathode is the same as embodiment 1.
Embodiment 5
The structure of highly reliable passive organic electroluminescent device described in the present embodiment is same as Example 2, and difference only exists
In the pixel segmenting structure of the second plate ITO layer is as shown in Figure 6.The selection of organic material and electron injection material, cathode
With embodiment 1.
Comparative example 1
128 × 64 screen bodies described in this comparative example are the structure of PMOLED prior art routine, and anode and cathode designs such as
Shown in attached drawing 2.Processing technology is similar to Example 1, but is free of current-limiting layer and second plate layer.Organic material and electronics note
Enter the selection of material, cathode with embodiment 1.
Comparative example 2
128 × 64 screen bodies described in this comparative example are the structure of PMOLED prior art routine, and anode and cathode designs such as
Shown in attached drawing 2.Processing technology is similar to Example 3, but is free of second plate layer.
The selection of 3 organic material of comparative example and electron injection material, cathode is the same as embodiment 1.
This comparative example is similar to the embodiment 2, and ITO is not only done segmentation design.
Experimental example
It detects, and is recorded in down according to device performance of the art methods to each embodiment and comparative example
Table.
It can be seen that the comparative example 1 for being not introduced into current-limiting layer screen body from above-mentioned statistics, device general defect rate is high.
And be introduced into current-limiting layer and obtain in comparative example 2, device defects are then substantially reduced, but because current-limiting layer is matched with organic layer and asked
Topic, leads to operating voltage height.As it can be seen that scheme of the present invention on the basis of current-limiting layer is arranged, further uses second
The screen body of anode layer, operating voltage are substantially reduced.Pass through segmentation in addition, can be seen that from the comparison of comparative example 3 and embodiment 2
Pixel further decreases corresponding region electric current, can further decrease defect level.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (8)
1. a kind of highly reliable passive organic electroluminescent device, including substrate, and forms anode layer on the substrate, has
Machine functional layer and cathode layer, which is characterized in that the device further include current-limiting layer and with the organic function layer work content
The material layer that number matches, the resistivity of the current-limiting layer are 1.0 × 101-1.0×103Ω/□;
The anode layer successively includes first anode layer, current-limiting layer and second plate layer along the close orientation substrate;
Alternatively,
The cathode layer successively includes the first cathode layer, current-limiting layer and the second cathode layer along the separate orientation substrate;
The second plate layer and second cathode layer are the material layer to match with the organic function layer work function;
The anode layer and the organic luminous layer of the cathode layer intersection region form screen body light emitting pixel, the second plate layer
Light emitting pixel structure several subpixel areas less than visual range, each son are divided into according to its concrete application field
The area of pixel region is between (10-5000) μ m (10-5000) um.
2. highly reliable passive organic electroluminescent device according to claim 1, which is characterized in that form the electric current limit
The material of preparative layer includes the composite wood of metal oxide, organic polymer, small organic molecule, nano material or above-mentioned material composition
Material.
3. highly reliable passive organic electroluminescent device according to claim 2, which is characterized in that the first anode layer
Surface resistance<20 Ω/, the material for forming the second plate layer is work function>4.5eV metal oxide, metal or to have
Organic polymeric material;Alternatively,
The material for forming first cathode layer is low-work-function material, formed second cathode layer material be surface resistance <
20 Ω/ conductive material.
4. highly reliable passive organic electroluminescent device according to claim 3, which is characterized in that the second plate layer
It is consistent with the figure of the first anode layer.
5. highly reliable passive organic electroluminescent device according to claim 1-4, which is characterized in that each described
Subpixel area independent of each other includes hexagonal structure, triangular structure of right angle, square structure or irregular figure knot
Structure.
6. highly reliable passive organic electroluminescent device according to claim 5, which is characterized in that each sub-pixel area
Divided by rule and in regularly arranged in domain.
7. a kind of method for preparing highly reliable passive organic electroluminescent device described in any one of claims 1-6, feature
It is, includes the following steps:
(1) the selected substrate is made according to prior art conventional method, and forms selected first anode layer;
(2) current-limiting layer of selected material is prepared in the first anode layer surface according to prior art conventional method;
(3) the second plate layer is prepared in the current limit layer surface according to prior art conventional method, and ensured described
First anode layer is consistent with the figure of the second plate layer;
(4) organic function layer and the cathode layer is conventionally made, and encapsulates the preparation for completing screen body;Alternatively,
(1) the selected substrate is made according to prior art conventional method, and forms selected anode layer;
(2) organic function layer is conventionally made, and shows to form second cathode in the organic function layer
Layer;
(3) current-limiting layer of selected material is prepared in the second cathode layer surface according to prior art conventional method;
(4) first cathode layer is prepared in the current limit layer surface according to prior art conventional method, and encapsulates completion
Shield the preparation of body;Alternatively,
(1) the selected substrate is made according to prior art conventional method, and forms selected cathode layer;
(2) organic function layer is conventionally made, and shows to form the second plate in the organic function layer
Layer;
(3) current-limiting layer of selected material is prepared in the second plate layer surface according to prior art conventional method,
And ensure that the first anode layer is consistent with the figure of the second plate layer;
(4) first anode layer is prepared in the current limit layer surface according to prior art conventional method, and encapsulates completion
Shield the preparation of body;Alternatively,
(1) the selected substrate is made according to prior art conventional method, and forms selected first cathode layer;
(2) current-limiting layer of selected material is prepared in the first cathode layer surface according to prior art conventional method;
(3) second cathode layer is prepared in the current limit layer surface according to prior art conventional method;
(4) organic function layer and the anode layer is conventionally made, and encapsulates the preparation for completing screen body.
8. the method for highly reliable passive organic electroluminescent device, feature described in preparation according to claim 7 exist
In, the method also includes the structure and arrangement mode according to the selected subpixel area, to the second plate layer into
The step of row segmentation.
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CN110767674B (en) * | 2018-08-06 | 2022-05-17 | 苏州清越光电科技股份有限公司 | Display panel, display screen and display terminal |
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