CN207977352U - A kind of Organic Light Emitting Diode - Google Patents
A kind of Organic Light Emitting Diode Download PDFInfo
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- CN207977352U CN207977352U CN201721486136.3U CN201721486136U CN207977352U CN 207977352 U CN207977352 U CN 207977352U CN 201721486136 U CN201721486136 U CN 201721486136U CN 207977352 U CN207977352 U CN 207977352U
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Abstract
The application provides a kind of Organic Light Emitting Diode (OLED) with ion implanted layer.In the OLED of the application, the layer structure of subsequent deposition is finer and close on ion implanted layer, has few pinhole number so that the OLED of the application is better than existing OLED in terms of luminous efficiency and binding force.
Description
Technical field
This application involves the fields Organic Light Emitting Diode (OLED), and in particular to a kind of OLED with ion implanted layer and
Preparation method.
Background technology
Organic Light Emitting Diode（Organic Light-Emitting Diode, UIV OLED）Also known as organic electric laser
Display, organic luminous semiconductor have self-luminous, wide viewing angle, almost infinite high contrast, fast compared with low power consumption, high reaction
The advantages that spending, thus it is widely used in mobile phone, DV, DVD player, personal digital assistant（PDA）, laptop, vapour
Vehicle sound equipment and TV.
The OLED multilayered structures of the prior art are as shown in Figure 1, it may include anode (Anode), hole injection layer (HIL), sky
Cave transport layer (HTL), luminescent layer (EM), electron transfer layer (ETL), electron injecting layer (EIL) and metallic cathode (Cathode).
How many layer material selected actually in design, it must be depending on layers of material energy rank distribution situation.It is using the purpose of multilayered structure
In order to cause the energy scalariform state such as stepped-style, the hole and electronics that are provided respectively from anode and cathode is made to be easier to be transmitted to
Luminescent layer, in conjunction with then releasing photon.And in the use of material, doping can be added in right amount to adjust required energy scalariform state.
Traditional OLED preparation processes are as follows：
1. ITO is deposited on transparent flexible film or glass substrate using magnetron sputtering or evaporation coating technique, as sun
Pole；
2. being sequentially depositing hole injection layer, hole transport on the substrate that deposition has ito thin film using evaporation coating technique
Layer, organic luminous layer, electron transfer layer and electron injecting layer form multilayered structure；
3. evaporation coating or the magnetron sputtering technique deposit metal electrodes on multilayered structure are used, as cathode, most end form
At OLED.
The ito thin film and substrate binding force prepared using traditional magnetron sputtering or thermal evaporation coating process is poor, pin hole
It is more.Influence OLED device long term reliability in conjunction with force difference, particularly with flexible transparent conductive film, need ITO with it is soft
Property transparent membrane have higher binding force, to increase device lifetime.Pin hole mostly can be such that the resistivity of ito thin film improves, and reduce
Electric conductivity.
Similarly, traditional thermal evaporation plated film or magnetron sputtering technique make metal electrode and bring more pin hole, increase
Electrode resistance and work function, reduce electric conductivity, influence the characteristic of entire device, such as make OLED brightness deteriorations.In addition it can lead
It causes peel strength low, influences the reliability of OLED device.
Therefore, in the art, it is expected that realizing between anode and substrate and in metal electrode and such as electron injection
The pin hole of high-bond, reduction between layer or even pin-free and improved electric conductivity, to obtain performance raising
OLED。
Invention content
The one side of the application is to provide a kind of Organic Light Emitting Diode, which includes and substrate phase
The first adjacent adjacent layer and second adjacent layer adjacent with metallic cathode, it is characterised in that it is characterized in that having following at least one
A ion implanted layer：
(i) the first ion implanted layer being arranged on surface of the substrate towards first adjacent layer；
(ii) the second ion implanted layer being arranged on the surface of second adjacent layer towards the metallic cathode.
That is, the Organic Light Emitting Diode of the application can only have the first ion implanted layer, or only have second from
Both sub- implanted layer, or there are the first and second ion implanted layers simultaneously.
According to an embodiment, in the Organic Light Emitting Diode of the application, the doping of first ion implanted layer
Dosage is 1x1014ions/ cm2-1x1016ions/ cm2, the dopant dose of second ion implanted layer is 1x1014ions/
cm2-1x1016ions/ cm2。
According to another embodiment, in the Organic Light Emitting Diode of the application, first ion implanted layer and
The thickness of two ion implanted layers is respectively about 1nm-20nm, for example, about 3-15nm, or about 3-10nm, or about 5nm.
According to another embodiment, in the Organic Light Emitting Diode of the application, first adjacent layer is anode.
According to another embodiment, in the Organic Light Emitting Diode of the application, second adjacent layer is noted for electronics
Enter layer.
According to another embodiment, in the Organic Light Emitting Diode of the application, the anode is to pass through plasma
The conductive film that depositing operation is formed, such as ITO, AZO, preferably ITO.The conductive film can be transparent.
According to another embodiment, in the Organic Light Emitting Diode of the application, the metallic cathode passes through plasma
Body depositing operation is formed, and material can be selected from Mg, Ag, Al, Mo, Ca, Li or its alloy.
According to another embodiment, in the Organic Light Emitting Diode of the application, in first ion implanted layer
Doped ions are identical as the material category of the first adjacent layer, the Doped ions and metallic cathode in second ion implanted layer
Material category is identical.
According to another embodiment, in the Organic Light Emitting Diode of the application, mixed in first ion implanted layer
The metal types of heteroion include Sn, In or its alloy；The metal types of Doped ions include in second ion implanted layer
Mg, Ag, Al, Mo, Ca, Li or its alloy.
According to another embodiment, in the Organic Light Emitting Diode of the application, the baseplate material can be selected from glass,
PI films, PET film, LCP films.Substrate can be transparent.
According to another embodiment, the Organic Light Emitting Diode of the application is with the first ion implanted layer the case where
Under, the binding force between the substrate and first adjacent layer is more than 0.5N/m；With the second ion implanted layer the case where
Under, the binding force between the metallic cathode and second adjacent layer is more than 0.5N/m.
One example arrangement of the Organic Light Emitting Diode of the application is as shown in Figure 2.Wherein in glass or film substrate
On be provided with ITO sedimentaries as anode（That is, sedimentary 1）, substrate is adjacent with ITO sedimentaries, in table of the substrate towards ITO
The first ion implanted layer is provided on face.Multilayered structure is provided on ITO, since the side towards ITO, the multilayered structure
Include hole injection layer (HIL), hole transmission layer (HTL), luminescent layer (EM), electron transfer layer (ETL), electron injecting layer successively
(EIL).The metal electrode sedimentary as cathode is provided on multilayered structure（That is, sedimentary 2）, the EIL in multilayered structure
It is adjacent with metal electrode, the second ion implanted layer is provided on surfaces of the EIL towards metal electrode.
It should be understood that the Organic Light Emitting Diode of the application is not limited to specific structure shown in Fig. 2.Although for example, in example
The Organic Light Emitting Diode of middle the application has (i) substrate/first ion implanted layer/ITO sedimentaries, and (ii) EIL/ second
The two structures of ion implanted layer/deposit metal electrodes, but the Organic Light Emitting Diode of the application may not necessarily be provided simultaneously with institute
State two structures.In certain embodiments, Organic Light Emitting Diode can individually have structure (i), in certain embodiments,
Organic Light Emitting Diode can individually have structure (ii).
Other functional layers in addition to ITO sedimentaries can be provided on substrate.In the case, then substrate and other work(
Ergosphere is adjacent, and the first ion implanted layer is arranged on surface of the substrate towards other functional layers.
In addition, multilayered structure can further include one or more other functional layers, such as surface reforming layer, hole resistance
Barrier, electronic barrier layer etc..Therefore, in some embodiments, metal electrode can in multilayered structure in addition to EIL in addition
Functional layer it is adjacent.In the case, on the surface of the adjacent other functional plane to metal electrode setting second from
Sub- implanted layer.
According to an embodiment, in the Organic Light Emitting Diode of the application, hole injection layer may include that hole is isolated
Layer, organic matter layer two parts.The material of hole separation layer can be selected from transition metal oxide, such as MoO3、WO3、V2O5And its it is mixed
Close object.The material of organic matter layer can be selected from organic hole injection material customary in the art, such as tetrafluoro quinone bismethane
（F4TCNQ）Deng.
According to another embodiment, in the Organic Light Emitting Diode of the application, the material of hole transmission layer can be selected from
Triphenyl diamine class compound (TPD), N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines (NPB) and
Its mixture.
According to another embodiment, in the Organic Light Emitting Diode of the application, luminescent layer includes material of main part, fluorescence
Material and phosphor material.Material of main part can be selected from CBP, PVK, SimCP and its mixture.Fluorescent material may include：It can be selected from
The red fluorescence material of DCJTB, DCM and its mixture；It can be selected from the green fluorescence material of Alq3, QA, C545T and its mixture
Material；The blue fluorescent materials such as DPVBi.Phosphor material can be selected from precious metals complex and its mixture customary in the art.
According to another embodiment, in the Organic Light Emitting Diode of the application, the material of electron transfer layer can be selected from
Organic matter with the strong functional group of the electron-withdrawing abilities such as pyridine, phosphatization hydroxide, quinoline, triazole, such as Alq3, BCP, TBPI
Deng and one such or a variety of mixtures in any proportion.
According to another embodiment, in the Organic Light Emitting Diode of the application, the material of electron injecting layer can be selected from
LiF、Cs2O3, TiOx, MnO etc. and one such or a variety of mixtures in any proportion.
The another aspect of the application is a kind of method of manufacture Organic Light Emitting Diode, and this approach includes the following steps：
(a) plasma clean is carried out to substrate in vacuum chamber, ion is then carried out on the substrate surface of cleaning
Injection forms the first ion implanted layer；
(b) anode is formed on the first ion implanted layer obtained by step (a)；
(c) on the anode obtained by step (b), formation includes hole injection layer, hole transmission layer, organic luminous layer, electricity
The multilayered structure of sub- transport layer and electron injecting layer；
(d) ion implanting is carried out on the surface of the multilayered structure obtained by step (c), forms the second ion implanted layer；
(e) metallic cathode is formed on the second ion implanted layer obtained by step (d).
According to an embodiment, in the present processes, it is in the process conditions of step (a) intermediate ion injection：From
Sub- Implantation Energy 10-50keV, injection length 1-10min, injection target use Sn, In or its alloy.
According to another embodiment, in the present processes, the anode is to pass through plasma deposition process shape
At ito thin film.
According to another embodiment, in the present processes, it is in the process conditions of step (d) intermediate ion injection：
Ion implantation energy 10-50keV, injection length 1-10min, injection target use Mg, Ag, Al, Mo, Ca, Li or its alloy.
According to another embodiment, in the present processes, the metallic cathode passes through plasma deposition process
It is formed, the material of use can be selected from Mg, Ag, Al, Mo, Ca, Li or its alloy.
According to another embodiment, in the present processes, the substrate can be selected from glass, PI films, PET film, LCP
Film.
Also include one or more in the multilayered structure in the present processes according to another embodiment
Functional layer, such as surface reforming layer, electronic barrier layer, hole blocking layer.
According to another embodiment, in the present processes, the multilayered structure uses thermal evaporation coating process shape
At.
The Organic Light Emitting Diode and its manufacturing method of the application utilizes ion implanting and plasma deposition process, realizes
Few pin hole in OLED structure, to improve the performance of OLED device.
Technical scheme set forth below is to the influencing mechanism of OLED device performance, it should be understood that the application is not limited
In this theory：
Work function refers to the minimum energy moved on to an electronics from fermi level in 0K temperature needed for unlimited distance.Big portion
Divide the lumo energy of the organic material applied to OLED in 2.5 ~ 3.5eV, so work function is lower, injection barrier is lower, electricity
Son injection is easier, and the luminous efficiency of OLED device is higher.Work function is influenced by the surface defect of substance.As metal electricity
The surface defect of pole, pin hole quantity is more, and work function is higher, and is easily attacked by water and oxygen in pin hole, influences metal electrode
Service life.Pin hole quantity is fewer, then whole work function is lower, and the luminous efficiency of OLED is higher.The OLED of the application, which has, to be adopted
The ion implanted layer formed with injection method so that the follow-up layer structure deposited on it is finer and close, to realize few pin hole
Number.In the case where electrode material is selected, the luminous efficiency of the OLED of the application is far above existing OLED, and with preferably knot
With joint efforts.
Therefore, compared with prior art, the Organic Light Emitting Diode of the application and its manufacturing method at least have following excellent
Gesture：
● pinhole number is few, and surface defect reduces；
● electric conductivity improves, to enhance OLED brightness and current efficiency；
● binding force improves, and stability is stronger, and device lifetime is longer.
Description of the drawings
Fig. 1 is the structure of the OLED device of the prior art；
Fig. 2 is the structure of the OLED device of the application.
Specific implementation mode
The manufacturing process of the prior art
Magnetron sputtering or evaporation coating technique is used to deposit ITO on transparent flexible film or glass substrate first, as
Anode.Then evaporation coating technique is used to be sequentially depositing hole injection layer, hole transport on the substrate that deposition has ito thin film
Layer, organic luminous layer, electron transfer layer and electron injecting layer.Use evaporation coating or magnetron sputtering technique in electron injecting layer again
Upper deposit metal electrodes form OLED as cathode.
The manufacturing process of the application
First, glass or film substrate are put into vacuum chamber, chamber is carried out to be heated to 80 DEG C, is evacuated to vacuum degree
Higher than 3.0 × 10-3Pa leads to argon gas, makes vacuum degree 1.2 × 10-2Pa~4.5×10-2Pa ranges, open Hall source to substrate into
Row plasma clean, 800 ~ 1500V of cleaning voltage, 0.1 ~ 2A of electric current, 5 ~ 20min of scavenging period.
To after cleaning glass or film substrate carry out ion implanting, 10 ~ 50keV of ion implantation energy, injection length 1 ~
10min.Inject target using Sn, In and or both alloy.Form the first ion implanted layer.
It carries out plasma-deposited, using Sn and In alloys targets, is filled with O2, make vacuum degree 1.5 × 10-2Pa~3.0×10- 2Pa ranges, 10 ~ 50eV of sedimentary energy, 2 ~ 5min of sedimentation time.Form ito thin film.
Using thermal evaporation coating process, hole injection layer, hole transmission layer, organic light emission are respectively formed on ito thin film
Layer, electron transfer layer and electron injecting layer.
Metal ion is injected in electron injection layer surface using ion implantation technology, forms implanted layer 2, ion implantation energy
10 ~ 50keV, 1 ~ 10min of injection length.
Metal electrode is formed by plasma-deposited one layer of metal again.Inject the metal class used in metal and metal electrode
Type is Mg, Ag, Al, Mo, Ca and their mutual alloys.To obtain the OLED of the application.
Embodiment 1
The present embodiment OLED is manufactured according to the application manufacturing process, and the specific material and size of each section are as follows：
Substrate：Glass；
Anode material：Tin indium oxide（ITO）（10nm）；
Hole injection layer：Tetrafluoro quinone bismethane（F4TCNQ）（10nm）；
Hole transmission layer：N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines（NPB）（25nm）；
Organic luminous layer：4,4'- bis- (9- carbazoles) biphenyl（CBP）（20nm）；
Electron transfer layer：8-hydroxyquinoline aluminium（Alq3）(20nm)；
Electron injecting layer：LiF(50nm)；
Metallic cathode：CaAl alloys (100nm)；
First ion implanted layer：InSn alloys, thickness 5nm, dopant dose 5x1014ions/ cm2；
Second ion implanted layer：CaAl alloys, thickness 5nm, dopant dose 1.8x1014ions/ cm2。
Embodiment 2
The present embodiment OLED is manufactured according to the application manufacturing process, and the specific material and size of each section are as follows：
Substrate：PET film；
Anode material：Tin indium oxide（ITO）（15nm）；
Hole injection layer：Tetrafluoro quinone bismethane（F4TCNQ）（10nm）；
Hole transmission layer：N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines（NPB）（20nm）；
Organic luminous layer：4,4'- bis- (9- carbazoles) biphenyl（CBP）（25nm）；
Electron transfer layer：8-hydroxyquinoline aluminium（Alq3）(20nm)；
Electron injecting layer：LiF(40nm)；
Metallic cathode：MgAl alloys (80nm)；
First ion implanted layer：InSn alloys, thickness 4nm, dopant dose 2.5x1015ions/ cm2；
Second ion implanted layer：MgAl alloys, thickness 10nm, dopant dose 8x1015ions/ cm2。
Embodiment 3
The present embodiment OLED is manufactured according to the application manufacturing process, and the specific material and size of each section are as follows：
Substrate：PI films；
Anode material：Tin indium oxide（ITO）（12nm）；
Hole injection layer：Tetrafluoro quinone bismethane（F4TCNQ）（15nm）；
Hole transmission layer：N, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines（NPB）（25nm）；
Organic luminous layer：4,4'- bis- (9- carbazoles) biphenyl（CBP）（25nm）；
Electron transfer layer：8-hydroxyquinoline aluminium（Alq3）(25nm)；
Electron injecting layer：LiF(50nm)；
Metallic cathode：MgAg alloys (95nm)；
First ion implanted layer：InSn alloys, thickness 6nm, dopant dose 8x1014ions/ cm2；
Second ion implanted layer：MgAg alloys, thickness 8nm, dopant dose 3.6x1015ions/ cm2。
Performance comparison
By the OLED of the embodiment of the present application 1 and the OLED according to the manufacture of prior art manufacturing process（It is used and embodiment 1
Essentially identical material and structure, but there is no ion implanted layer）It is compared, the two performance is as shown in table 1.
Table 1
| The bond strength (N/mm) of substrate/anode | The bond strength (N/mm) of electron injecting layer/metallic cathode | Brightness (cd/cm2) | Current efficiency (cd/A) | |
| The OLED of embodiment 1 | 0.5 | 0.5 | ≥30 | ≥12000 |
| The OLED of the prior art | 0.3 | 0.3 | 25 | 10000 |
As it can be seen that the OLED device of the application has the bond strength significantly improved, while there is higher brightness and electric current
Efficiency.Brightness and current efficiency are to weigh the important parameter of OLED performances.Brightness refer to eye-observation to light intensity with observe
Area ratio, i.e., the luminous intensity of unit projection area, measuring instrument are spectroradiometer.Current efficiency is brightness and electric current
Ratio.OLED drives for electric current, and current density is bigger, and OLED device temperature increases, organic semiconductor reduced performance, reduces hair
Light efficiency.Excessively high current density can not only influence luminous efficiency, can also greatly shorten the service life of OLED.In other words, higher
Current efficiency shows that OLED has more preferably luminous intensity under certain current density, therefore the OLED of the application has more preferably
Luminous efficiency.
Claims (18)
1. a kind of Organic Light Emitting Diode, the Organic Light Emitting Diode include first adjacent layer adjacent with substrate and with metal the moon
The second extremely adjacent adjacent layer, it is characterised in that there is following at least one ion implanted layer：
(i) the first ion implanted layer being arranged on surface of the substrate towards first adjacent layer；
(ii) the second ion implanted layer being arranged on the surface of second adjacent layer towards the metallic cathode.
2. Organic Light Emitting Diode according to claim 1, wherein the dopant dose of first ion implanted layer is
1x1014ions/cm2-1x1016ions/cm2, the dopant dose of second ion implanted layer is 1x1014ions/cm2-
1x1016ions/cm2。
3. according to the Organic Light Emitting Diode of claims 1 or 2, wherein first ion implanted layer and the second ion implanted layer
Thickness be respectively 1nm-20nm.
4. Organic Light Emitting Diode according to claim 3, wherein first ion implanted layer and the second ion implanted layer
Thickness is respectively 3-15nm.
5. Organic Light Emitting Diode according to claim 3, wherein first ion implanted layer and the second ion implanted layer
Thickness is respectively 3-10nm.
6. Organic Light Emitting Diode according to claim 3, wherein first ion implanted layer and the second ion implanted layer
Thickness is respectively 5nm.
7. according to the Organic Light Emitting Diode of claims 1 or 2, wherein first adjacent layer is anode.
8. Organic Light Emitting Diode according to claim 7, wherein the anode is to be formed by plasma deposition process
Ito thin film.
9. according to the Organic Light Emitting Diode of claims 1 or 2, wherein second adjacent layer is electron injecting layer.
10. according to the Organic Light Emitting Diode of claims 1 or 2, wherein the metallic cathode passes through plasma deposition process
It is formed, material is selected from Mg, Ag, Al, Mo, Ca, Li or its alloy.
11. according to the Organic Light Emitting Diode of claims 1 or 2, wherein Doped ions in first ion implanted layer with
The material category of first adjacent layer is identical, the material category phase of the Doped ions in second ion implanted layer and metallic cathode
Together.
12. Organic Light Emitting Diode according to claim 8, wherein in first ion implanted layer Doped ions metal class
Type includes Sn, In or its alloy；In second ion implanted layer metal types of Doped ions include Mg, Ag, Al, Mo, Ca,
Li or its alloy.
13. Organic Light Emitting Diode according to claim 10, wherein in first ion implanted layer Doped ions metal
Type includes Sn, In or its alloy；In second ion implanted layer metal types of Doped ions include Mg, Ag, Al, Mo,
Ca, Li or its alloy.
14. according to the Organic Light Emitting Diode of claims 1 or 2, wherein the substrate is thin selected from glass, PI films, PET film, LCP
Film.
15. Organic Light Emitting Diode according to claim 7, wherein being provided between the anode and the metallic cathode more
Layer structure, which includes hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and electron injecting layer.
16. Organic Light Emitting Diode according to claim 15, wherein also including one or more another in the multilayered structure
Outer functional layer.
17. Organic Light Emitting Diode according to claim 16, wherein the other functional layer is selected from surface reforming layer, electronics
Barrier layer, hole blocking layer.
18. according to the Organic Light Emitting Diode of claims 1 or 2, wherein with the first ion implanted layer, it is described
Binding force between substrate and first adjacent layer is more than 0.5N/m；The case where with the second ion implanted layer
Under, the binding force between the metallic cathode and second adjacent layer is more than 0.5N/m.
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