CN107359255A - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN107359255A CN107359255A CN201611199123.8A CN201611199123A CN107359255A CN 107359255 A CN107359255 A CN 107359255A CN 201611199123 A CN201611199123 A CN 201611199123A CN 107359255 A CN107359255 A CN 107359255A
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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
- H10K50/171—Electron injection layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/16—Electron 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
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.The organic electroluminescence device includes substrate, cathode layer, microcavity adjustment layer, light emitting functional layer and the anode layer being cascading；Cathode layer is located at substrate；Microcavity adjustment layer is located on cathode layer, and the material of microcavity adjustment layer is inorganic, metal oxide material；There is luminescent layer, light emitting functional layer is stacked gradually with anode layer and is located on microcavity adjustment layer in light emitting functional layer.The problem of organic electroluminescence device exists for small molecule evaporation device when adjustment microcavity chamber is long, microcavity adjustment layer is made using inorganic metal oxide, it can be used for the chamber length for adjusting organic electroluminescence device, and electron injection and transport layer can be used as, forms a kind of printed form organic electroluminescence device of efficient stabilization.
Description
Technical field
The present invention relates to electroluminescent device field, more particularly, to a kind of organic electroluminescence device and its making side
Method.
Background technology
Organic Light Emitting Diode (OLED) due to active is luminous, visual angle is wide, fast response time, in light weight, color can
Adjust, can be flexible the advantages that, have broad application prospects, get more and more people's extensive concerning in fields such as display, illuminations.Measurement has
The parameter of machine lumination of light emitting diode performance mainly has：External quantum efficiency, current efficiency, driving voltage, device lifetime and colour purity
Degree.Microcavity resonance is a kind of effective ways for improving light and taking out, strengthening device efficiency, be applied to based on vacuum evaporation technology more
In the top emitting device of small molecule.Light is sent from translucent top electrodes in such top emitting device.In organic luminescent device
In, be usually used in microcavity resonance adjustment layer for organic molecule hole transmission layer, be primarily due to the material tool of hole transmission layer
There is higher mobility.This method for being used to adjust organic luminescent device micro-cavity structure deposits that there are still one in batch production technique
The problem of determining, such as：(1) metal mask plate distillation technique (Fine metal mask, FFM) is needed to use, adds and is produced into
This；(2) refractive index of organic molecule hole mobile material is limited (generally 1.5-1.7), thus needs that thicker sky is deposited
Hole transport materials, especially become apparent in red light emitting device, and thicker hole mobile material, which is deposited, to be meaned to be deposited
The increase of time, it can so increase pitch time (tact time).
The content of the invention
Based on this, it is necessary to which providing a kind of can improve device efficiency and be advantageous to reduced cost, reduce pitch time
Organic electroluminescence device and preparation method thereof.
A kind of organic electroluminescence device, including substrate, cathode layer, microcavity adjustment layer, the luminous work(being cascading
Ergosphere and anode layer；The cathode layer is located at the substrate；The microcavity adjustment layer is located on the cathode layer, described
The material of microcavity adjustment layer is inorganic, metal oxide material；There is luminescent layer, the lighting function in the light emitting functional layer
Layer is stacked gradually with the anode layer and is located on the microcavity adjustment layer.
In one of the embodiments, the cathode layer is the electrode layer of patterning；The microcavity adjustment layer is correspondingly arranged at
On the area of the pattern of the cathode layer of patterning；The light emitting functional layer includes the luminescent layer of at least two colors；It is corresponding different
The thickness of the microcavity adjustment layer of the luminescent layer of color is different.
In one of the embodiments, the light emitting functional layer includes red light luminescent layer, green light emitting layer and blue light emitting
Layer；The microcavity that the thickness of the microcavity adjustment layer of the corresponding red light luminescent layer is more than the corresponding green light emitting layer is adjusted
The thickness of flood, and the thickness of the microcavity adjustment layer of the corresponding green light emitting layer is more than the corresponding blue light-emitting
The thickness of the microcavity adjustment layer.
In one of the embodiments, the thickness of the microcavity adjustment layer of the corresponding red light luminescent layer for 75~
90nm；
The thickness of the microcavity adjustment layer of the corresponding green light emitting layer is 65~75nm；
The thickness of the microcavity adjustment layer of the corresponding blue light-emitting is 50~65nm.
In one of the embodiments, the inorganic, metal oxide material is selected from ZnO, TiO2、MgO、ZrO2And HfO2In
One or more mixtures.
In one of the embodiments, the organic electroluminescence device also include positioned at the microcavity adjustment layer with it is described
Interface-modifying layer between light emitting functional layer, the material of the interface-modifying layer is electron injection material.
In one of the embodiments, the thickness of the interface-modifying layer is 5~10nm.
In one of the embodiments, the light emitting functional layer also includes between the luminescent layer and the anode layer
Electronic barrier layer, at least one functional layer in hole transmission layer and hole injection layer.
In one of the embodiments, the organic electroluminescence device also includes inorganic on the anode layer
The light removing layer of oxide, the thickness of the smooth removing layer is 40~60nm.
A kind of preparation method of organic electroluminescence device, comprises the following steps：
The coating photoresist on the substrate of the cathode layer with patterning, on the white space cover of the cathode layer of patterning
Light shield, it is exposed, develops, the photoresist on the cathode layer is removed, retain the photoresist of the white space, is formed recessed
Groove；
The precursor solution of inorganic oxide material is printed on cathode layer in the groove, after the completion of printing, is carried out
Heat drying processing, forms microcavity adjustment layer on the cathode layer；
The light emitting functional layer with luminescent layer is formed in the microcavity adjustment layer；
Anode layer is formed on the light emitting functional layer.
The problem of above-mentioned organic electroluminescence device exists for small molecule evaporation device when adjustment microcavity chamber is long, uses
Inorganic metal oxide makes microcavity adjustment layer, can be used for the chamber length for adjusting organic electroluminescence device, and can make
For electron injection and transport layer, a kind of printed form organic electroluminescence device of efficient stabilization is formed.In addition, the microcavity is adjusted
Flood can also strengthen the ability of the barrier water oxygen of device, extend its service life, and advantageously reduce organic electroluminescence
The pitch time of the evaporation of part, increase output, reduce cost.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an embodiment.
Embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to relevant drawings.In accompanying drawing
Give presently preferred embodiments of the present invention.But the present invention can realize in many different forms, however it is not limited to this paper institutes
The embodiment of description.On the contrary, the purpose for providing these embodiments is to make the understanding to the disclosure more thorough
Comprehensively.
It should be noted that when element is referred to as " being located at " another element, it can directly on another element or
There may also be element placed in the middle by person.When an element is considered as " connection " another element, it can be directly to
Another element may be simultaneously present centering elements.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
The arbitrary and all combination of the Listed Items of pass.
As shown in figure 1, the organic electroluminescence device 10 of an embodiment includes substrate 11, cathode layer 12, microcavity adjustment
Layer 13, light emitting functional layer 14 and anode layer 15.The organic electroluminescence device 10 is inverted type light-emitting device, and its cathode layer 12 leans on
Nearly substrate 11, anode layer 15 is away from substrate 11.
Substrate 11 is used to carry other structures layer, and the other structures of display device.Substrate 11 can be passive matrix
Type (PM) shows that substrate or active array type (AM) show substrate.Wherein, active array type shows that substrate includes substrate and is located at
The thin film transistor (TFT) (TFT) on another surface of substrate (i.e. the surface relative with the surface provided with cathode layer 12).Substrate can be firm
Property substrate or flexible base board.Rigid substrates can be ceramic material or all kinds of glass materials etc..Flexible base board can be polyamides Asia
Amine film (PI) and its derivative, PEN (PEN), PEP (PEP) or diphenylene
Ether resin etc..
Cathode layer 12 is located on substrate 11.In the present embodiment, cathode layer 12 is transparent electrode layer.Cathode layer 12
Material may be selected from ITO, AZO, TZO, nano-silver thread film or graphene etc..Further, in the present embodiment, the cathode layer 12
It is the electrode layer of patterning.The processing procedure of patterning can be realized by photoetching process.The cathode layer 12 of patterning has pattern
Region (i.e. the region provided with electrode material) and white space.
Microcavity adjustment layer 13 is correspondingly arranged on the area of the pattern of cathode layer 12 of patterning.The material of microcavity adjustment layer 13
For inorganic, metal oxide material, such as ZnO, TiO are selected from2、MgO、ZrO2And HfO2In one or more mixtures.
Light emitting functional layer 14 is located on microcavity adjustment layer 13.There is luminescent layer in light emitting functional layer 14.Corresponding pattern
Cathode layer 12, light emitting functional layer 14 includes the luminescent layer of at least two colors.In the present embodiment, light emitting functional layer 14 is wrapped
Include red light luminescent layer, green light emitting layer and blue light-emitting.Red light luminescent layer, green light emitting layer and blue light-emitting correspond to respectively
It is located on different microcavity adjustment layer 13.
In the present embodiment, the material of the microcavity adjustment layer 13 of the luminescent layer of corresponding different colours can be with identical or not
Together, but thickness is different, specifically, the thickness of the microcavity adjustment layer 13 of corresponding red light luminescent layer is more than the micro- of corresponding green light emitting layer
The thickness of intonation flood 13, and the thickness of the microcavity adjustment layer 13 of corresponding green light emitting layer is more than the microcavity of corresponding blue light-emitting
The thickness of adjustment layer 13, the thickness of the microcavity adjustment layer 13 of such as corresponding red light luminescent layer can be but be not limited to 75~90nm, excellent
Elect 80nm as；The thickness of the microcavity adjustment layer 13 of corresponding green light emitting layer can be but be not limited to 65~75nm, preferably 70nm；
The thickness of the microcavity adjustment layer 13 of corresponding blue light-emitting can be but be not limited to 50~65nm, preferably 60nm.
The light transmittance of microcavity adjustment layer 13 is preferably not less than 85%, not influence the light transmission of device.
Further, in the present embodiment, the organic electroluminescence device 10 is also included positioned at microcavity adjustment layer 13 and hair
Interface-modifying layer 16 between light functional layer 14.The material of interface-modifying layer 16 is that can strengthen the electronics note for improving electron injection
Enter material, the modifying interface material of different type evaporation type or printed form, which such as may be selected, improves electron injection, such as evaporation type
NaF、CsF、CsCO3Deng or printed form PEIE, PEO etc..The thickness of interface-modifying layer can be, but not limited to as 5~10nm.
Anode layer 15 is located on light emitting functional layer 14.The anode layer 15 of present embodiment is translucent electrode layer, institute
Material can be, but not limited to magnesium, aluminium, silver-colored silver-base alloy etc., and such as Mg and Ag alloy, wherein Mg and Ag weight ratio can be with
But it is not limited to 1:9.
Light emitting functional layer 14 can also include electronic barrier layer, the hole transmission layer between luminescent layer and anode layer 15
And at least one functional layer in hole injection layer.Hole injection layer is used for the film-forming quality for improving subsequent organic layers, and has
Help inject holes into hole transmission layer or luminescent layer.Material for hole injection layer includes but is not limited to porphyrin chemical combination
Thing, fluorocarbon polymer etc..Hole transmission layer contains at least one hole transport compound, such as aromatic uncle amine.Further, institute
State aromatic uncle amine be containing it is at least one at least one trivalent nitrogen atom only be connected with carbon atom and above-mentioned carbon atom be fragrant
The compound of ring, aromatic uncle amine can be arylamines, such as arylamine of monoarylamine, diaryl amine or polymerization etc..Hole passes
Defeated layer can be formed by the mixture of a kind of aromatic tertiary amine compound or a variety of aromatic tertiary amine compounds.Another kind of hole transmission layer
Material includes polycyclc aromatic compound.Further, it is possible to use the hole mobile material of polymerization is for example poly- (N- vinyl carbazoles)
(PVK), polythiophene, polypyrrole, or Copolymer, such as poly- (3,4- Ethylenedioxy Thiophene ester)/poly- (4- styrene sulfonates)
(PEDOT/PSS) etc..
In the present embodiment, the organic electroluminescence device 10 also includes the inorganic oxide on anode layer 15
Light removing layer 17.The material of light removing layer 17 can be selected from least one of following inorganic oxide material：MoO3、WO3And
V2O5.The thickness of light removing layer 17 is 40~60nm.Light removing layer 17 can optimize the luminous efficiency of red, green, blue device, and
And the ability that device stops water oxygen can be strengthened as water oxygen barrier layer, to extend the service life of device.
In addition, the organic electroluminescence device 10 also includes encapsulation cover plate 18.Encapsulation cover plate 18 located at light removing layer 17 it
On to encapsulate the internal element of whole organic electroluminescence device 10, strengthen water oxygen blocking capability, ensure the stable performance of device
Property.
Present embodiment additionally provides a kind of preparation method of organic electroluminescence device, and it comprises the following steps：
Step 1：The coating photoresist on the substrate of the cathode layer with patterning, to the blank of the cathode layer of patterning
The upper light shield of region cover, is exposed, develops, the photoresist on cathode layer is removed, retain the photoresist of white space, formed recessed
Groove.
Photoresist can be used but be not limited to such as spin coating, slot coated mode is coated with.After exposure, development, also wrap
Include the step of being heat-treated the substrate of coating photoresist.
Step 2：The precursor solution of inorganic oxide material is printed on cathode layer in groove, after the completion of printing, is entered
The processing of row heat drying, forms microcavity adjustment layer on cathode layer.
The mode of the preferred inkjet printing of mode of printing.
Step 3：The light emitting functional layer with luminescent layer is formed in microcavity adjustment layer.
Step 4：Anode layer is formed on light emitting functional layer.
It is specific embodiment part below.
The flow that the present embodiment makes organic electroluminescence device is as follows：
(1) clean：The substrate of cathode layer with patterning is subjected to removing photoresistance successively, washes, is dried for standby.
(2) preparation of microcavity adjustment layer：
(i) on substrate about 1 μm of spin coating a layer thickness photoresist, use light shield corresponding with red, green, blue pixel openings
It is exposed, after development, 20min is heat-treated at 200 DEG C, forms the substrate of patterning, wherein, the cathode layer of patterning
Area of the pattern does not have photoresist, and the photoresist of white space is retained, thus forms the groove knot around the area of the pattern
Structure.
(ii) substrate that will be patterned into is placed on printing machine platform, respectively corresponding to red, green, blue pixel on cathode layer
Print different-thickness inorganic oxide precursor solution, printing complete after, at 150-200 DEG C be heat-treated 30min~
1h (selects different process conditions according to different materials), and forming the transparent oxide of different-thickness, (red, green, blue pixel is corresponding
The thickness of oxide be respectively 80nm, 70nm, 60nm), solution can be ZnO, TiO2、MgO、ZrO2、HfO2At least one of
The precursor solution of inorganic, metal oxide.It is preferred that TiO2、ZrO2、TiO2:HfO2Red, green, blue pixel is corresponded to respectively.This layer system
The substrate got ready can in advance be prepared and stored for future use.
(3) preparation of interface-modifying layer：Improve electricity using the modifying interface material of different types of evaporation type or printed form
Son injection, such as NaF, CsF, CsCO3(evaporation type) or PEIE, PEO (printed form), thickness are 5~10nm.
(4) preparation of luminescent layer：Then the mode of use doping is being total to corresponding to blue light pixel region in microcavity adjustment layer
Luminescent layer CBP thick one layer of 20nm of evaporation:FIrpic, wherein FIrpic doping ratio are 8% (weight ratio), and speed is deposited in both
Rate is controlled asWithVacuum is 2 × 10-4Pa, form blue light-emitting；Then in green glow pixel region
The thick luminescent layer CBP of one layer of 40nm are deposited in corresponding microcavity adjustment layer:Ir(ppy)3, wherein Ir (ppy)3Doping ratio is 6%
(weight ratio), both are controlled as evaporation rateWithVacuum is 2 × 10-4Pa；Finally in feux rouges pixel
The thick luminescent layer CBP of one layer of 55nm are deposited corresponding to region in microcavity adjustment layer:Ir(piq)3, wherein Ir (piq)3Doping ratio
For 5% (weight ratio), both are controlled as evaporation rateWithVacuum is 2 × 10-4Pa。
(5) preparation of hole transmission layer：Then the thick hole mobile material CBP of one layer of 30nm are deposited, evaporation rate isVacuum is 2 × 10-4Pa。
(6) preparation of hole injection layer：The thick hole-injecting material MoO of one layer of 10nm are deposited on ITO3, evaporation rate
ForVacuum is 2 × 10-4Pa。
(7) preparation of metal anode：The thick semitransparent anode Mg of one layer of 15nm are finally deposited:Ag alloys, wherein Mg:Ag's
Weight ratio is 1:9, both are controlled as evaporation rateWithVacuum is 2 × 10-4Pa。
(8) preparation of light removing layer：
One layer of 40~60nm thickness MoO of hydatogenesis on semitransparent anode3、WO3Or V2O5As light removing layer, evaporation
Speed all controlsVacuum is 2 × 10-4Pa。
(9) encapsulate：Filled with N2Glove box in using UV glue be bonded cover-plate glass and substrate, then UV consolidates
Change, complete encapsulation.Also separately drier can be attached in cap to adsorb the moisture of residual, improve packaging effect.
Detected by testing, the organic electroluminescence device of the inverted structure of the present embodiment, because setting microcavity on negative electrode
Adjustment layer, can adjust the injection and transmission of electronics, and its luminous efficiency is obviously improved than traditional organic electroluminescence device.
The problem of above-mentioned organic electroluminescence device exists for small molecule evaporation device when adjustment microcavity chamber is long, uses
Inorganic metal oxide makes microcavity adjustment layer, can be used for the chamber length for adjusting organic electroluminescence device, and can make
For electron injection and transport layer, a kind of printed form organic electroluminescence device of efficient stabilization is formed.In addition, the microcavity is adjusted
Flood can also strengthen the ability of the barrier water oxygen of device, extend its service life, and advantageously reduce organic electroluminescence
The pitch time of the evaporation of part, increase output, reduce cost.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of organic electroluminescence device, it is characterised in that including substrate, cathode layer, the microcavity adjustment being cascading
Layer, light emitting functional layer and anode layer；The cathode layer is located at the substrate；The microcavity adjustment layer is located at the cathode layer
On, the material of the microcavity adjustment layer is inorganic, metal oxide material；There is luminescent layer in the light emitting functional layer, it is described
Light emitting functional layer is stacked gradually with the anode layer and is located on the microcavity adjustment layer.
2. organic electroluminescence device as claimed in claim 1, it is characterised in that the cathode layer is the electrode of patterning
Layer；On the area of the pattern for the cathode layer that the microcavity adjustment layer is correspondingly arranged at patterning；The light emitting functional layer is included at least
The luminescent layer of two kinds of colors；The thickness of the microcavity adjustment layer of the luminescent layer of corresponding different colours is different.
3. organic electroluminescence device as claimed in claim 2, it is characterised in that the light emitting functional layer includes red light-emitting
Layer, green light emitting layer and blue light-emitting；The thickness of the microcavity adjustment layer of the corresponding red light luminescent layer is more than corresponding institute
State the thickness of the microcavity adjustment layer of green light emitting layer, and the thickness of the microcavity adjustment layer of the corresponding green light emitting layer
More than the thickness of the microcavity adjustment layer of the corresponding blue light-emitting.
4. organic electroluminescence device as claimed in claim 3, it is characterised in that correspond to the described micro- of the red light luminescent layer
The thickness of intonation flood is 75~90nm；
The thickness of the microcavity adjustment layer of the corresponding green light emitting layer is 65~75nm；
The thickness of the microcavity adjustment layer of the corresponding blue light-emitting is 50~65nm.
5. organic electroluminescence device as claimed in claim 1, it is characterised in that the inorganic, metal oxide material is selected from
ZnO、TiO2、MgO、ZrO2And HfO2In one or more mixtures.
6. organic electroluminescence device as claimed in claim 1, it is characterised in that also include positioned at the microcavity adjustment layer with
Interface-modifying layer between the light emitting functional layer, the material of the interface-modifying layer is electron injection material.
7. organic electroluminescence device as claimed in claim 6, it is characterised in that the thickness of the interface-modifying layer be 5~
10nm。
8. such as organic electroluminescence device according to any one of claims 1 to 7, it is characterised in that the light emitting functional layer
Also include in electronic barrier layer between the luminescent layer and the anode layer, hole transmission layer and hole injection layer extremely
Few One function layer.
9. the organic electroluminescence device as described in any one of claim 1~7, it is characterised in that also include being located at the sun
The light removing layer of inorganic oxide on the layer of pole, the thickness of the smooth removing layer is 40~60nm.
10. a kind of preparation method of organic electroluminescence device, it is characterised in that comprise the following steps：
The coating photoresist on the substrate of the cathode layer with patterning, to the white space cover glazing of the cathode layer of patterning
Cover, is exposed, develops, and the photoresist on the cathode layer is removed, and retains the photoresist of the white space, is formed recessed
Groove；
The precursor solution of inorganic oxide material is printed on cathode layer in the groove, after the completion of printing, is heated
Drying process, microcavity adjustment layer is formed on the cathode layer；
The light emitting functional layer with luminescent layer is formed in the microcavity adjustment layer；
Anode layer is formed on the light emitting functional layer.
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| WO2019228212A1 (en) * | 2018-05-31 | 2019-12-05 | 京东方科技集团股份有限公司 | Display panel, and display device |
| CN112582563A (en) * | 2020-12-14 | 2021-03-30 | 昆山国显光电有限公司 | Light emitting device, method of manufacturing the same, and light emitting display apparatus |
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| CN105720081A (en) * | 2016-02-24 | 2016-06-29 | 京东方科技集团股份有限公司 | Organic light-emitting diode array substrate, display device and manufacturing method |
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| CN103872087A (en) * | 2012-12-14 | 2014-06-18 | 乐金显示有限公司 | Organic light emitting diode display and method for fabricating the same |
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| CN108279540A (en) * | 2018-02-01 | 2018-07-13 | 深圳市光羿科技有限公司 | A kind of inorganic, metal oxide ion storage layer, its cryogenic fluid processing method and purposes |
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| CN107359255B (en) | 2019-08-09 |
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