CN109390489A - Light emitting diode and the preparation method and application thereof - Google Patents
Light emitting diode and the preparation method and application thereof Download PDFInfo
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- CN109390489A CN109390489A CN201710664425.6A CN201710664425A CN109390489A CN 109390489 A CN109390489 A CN 109390489A CN 201710664425 A CN201710664425 A CN 201710664425A CN 109390489 A CN109390489 A CN 109390489A
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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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/82—Cathodes
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/852—Arrangements for extracting light from the devices comprising a resonant cavity structure, e.g. Bragg reflector pair
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of light emitting diodes and its preparation method and application.Light emitting diode of the present invention includes anode and cathode and the luminescence unit that is incorporated between the anode and cathode, the anode includes the first metal oxide layer, graphene layer and the second metal oxide layer for stacking gradually combination, and first metal oxide layer or the second metal oxide layer are combined with luminescence unit stacking.Anode contained by light emitting diode of the present invention is sandwich composite, realizes the light extraction efficiency for improving above-mentioned light emitting diode, and then increase photoelectric efficiency, the electrical stability and mechanical stability of anode guarantee the stabilization of above-mentioned lifetime of LED.Preparation method ensure that the electrical stability and mechanical stability of the light emitting diode of preparation.Its application includes applying in middle display screen or solid-state lighting lamp.
Description
Technical field
The invention belongs to field of display technology, and in particular to a kind of light emitting diode and preparation method thereof and display screen are solid
State illuminator.
Background technique
In recent years, with the fast development of display technology, such as using semiconductor material as the light emitting diode of luminescent layer
(QLED) it has received widespread attention.
Since semiconductor has the humorous optico-electronic properties of size adjustable, it is widely used in light emitting diode, too
Positive energy battery and biological fluorescent labelling.Synthetic technology passes through development in more than 20 years, and people can synthesize various high quality
Nano material, photoluminescence efficiency can achieve 85% or more.Due to luminous, the luminous line width with dimension adjustable
The features such as narrow, photoluminescence efficiency is high and thermal stability, therefore be great latent using the light emitting diode (QLED) as luminescent layer
The next-generation display of power and solid-state lighting light source.Light emitting diode (QLED) is because having high brightness, low-power consumption, wide colour gamut, Yi Jia
Many advantages, such as work, obtains extensive concern and research in illumination and display field in recent years.By the development of many years, QLED
Technology obtains huge development.From the point of view of the documents and materials of open report, red and green QLED outer amount highest at present
Sub- efficiency alreadys exceed or close to 20%, shows the limit of the internal quantum efficiency of red green QLED actually already close to 100%.
In QLED device, the 20% of the light that electron-hole recombinations issue can launch device with light-permeable transparent film and by
Silicon photo diode detects, and the light of residue 80% can be because the reasons such as matrix scattering not be launched and cannot be connect by silicon light diode
By.Therefore, the loss of light in device how is reduced, improving light emission rate is that the current industry has been working hard the technology of solution and asks
Topic.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of light emitting diode and its preparation side are provided
Method, to solve existing light emitting diode, there are light loss height, the low technical problems of light emission rate.
Another object of the present invention is to provide a kind of display device or solid-state lighting lamp, with solve existing display device or
Solid-state lighting lamp leads to display effect or illumination since contained light emitting diode is low there are light loss height and light emission rate
The undesirable technical problem of effect.
In order to achieve the above-mentioned object of the invention, one aspect of the present invention provides a kind of light emitting diode.The light emitting diode
Including anode and cathode and the luminescence unit being incorporated between the anode and cathode, the anode or cathode includes successively layer
Folded the first metal oxide layer, graphene layer and the second metal oxide layer combined, and first metal oxide layer or
Second metal oxide layer is combined with luminescence unit stacking.
Another aspect of the present invention provides a kind of preparation method of light emitting diode of the present invention.The preparation method includes
The step of preparing anode or cathode as follows:
It is sequentially depositing the first metal oxide layer, graphene layer in matrix layer surface or luminescence unit surface, by annealing
The second metal oxide layer is deposited on the graphene layer surface after processing；Or
It is sequentially depositing the second metal oxide layer, graphene layer in matrix layer surface or luminescence unit surface, by annealing
The first metal oxide layer is deposited on the graphene layer surface after processing.
Another aspect of the invention provides a kind of display screen or solid-state lighting lamp.The display screen or solid-state lighting lamp
Tool contains light emitting diode of the present invention or the light emitting diode prepared by preparation method of the present invention.
Compared with prior art, anode or cathode contained by light emitting diode of the present invention is using the first metal oxide
Layer/graphene layer/second metal oxide layer sandwich composite, cooperates with so that metal oxide layer is played with graphene layer
Effect, specifically metal oxide and graphene form small optical microcavity, and microcavity resonance effects occurs, and realize that raising is above-mentioned
The light extraction efficiency of light emitting diode, and then increase photoelectric efficiency.Meanwhile the electrical stability of metal oxide and mechanically stable
Property is preferable, plays the role of the protective layer to graphene layer, increases the electrical stability and mechanical stability of the anode of composite construction,
Guarantee the stabilization of above-mentioned lifetime of LED.
Above-mentioned light emitting diode sequentially forms the first metal oxide layer/graphene layer/second metal oxygen using sedimentation
The sandwich composite anode or cathode of compound layer ensure that anode or yin so that anode or cathode structural behaviour is stablized
Synergistic effect extremely between contained metal oxide layer and graphene layer, specifically ensure that metal oxide and graphene shape
At micro-optics microcavity, play microcavity resonance effects, improve the light extraction efficiency of light emitting diode, while being also effectively ensured
The electrical stability and mechanical stability of anode or cathode.In addition, above-mentioned preparation method process conditions are easily-controllable, preparation ensure that
Anode or cathode and light emitting diode electrical stability and mechanical stability.
Above-mentioned display screen or solid-state lighting lamp due to containing aforementioned present invention light emitting diode, luminous damage
Small, light emission rate height is lost, and uses stable working performance, long service life.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of light emitting diode of the embodiment of the present invention；
Fig. 2 is light emitting diode another kind structural schematic diagram of the embodiment of the present invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
(1) light emitting diode
On the one hand, the embodiment of the present invention provides a kind of light emitting diode that light extraction efficiency is high.The light emitting diode construction
As shown in Figure 1, 2 comprising anode 10 and cathode 30 and the luminescence unit 20 being incorporated between the anode 10 and cathode 30.
Wherein, anode 10 or cathode 30 can be used as light-emitting surface.
In one embodiment, when anode 10 is as light-emitting surface, 10 structure of anode is as shown in Figure 1 comprising stacks gradually knot
The first metal oxide layer 11, graphene layer 12 and the second metal oxide layer 13 closed.It is pressed from both sides using two metal oxide layers
If the sandwich composite of graphene layer, so that in metal oxide in metal oxide layer 11 and 13 and graphene layer 12
Graphene forms small optical microcavity, plays and microcavity resonance effects occurs, and realizes that the light for improving above-mentioned light emitting diode takes out
Efficiency, and then increase photoelectric efficiency, it is also both that above-mentioned metal oxide layer 11 and 13 and graphene layer 12 play synergistic effect in fact
Now improve the light extraction efficiency of above-mentioned light emitting diode.In addition, in the sandwich composite of anode 10 as shown in Figure 1, metal
The electrical stability and mechanical stability of oxide are preferable, play the role of the protective layer to graphene layer 12, increase composite construction
Anode 10 electrical stability and mechanical stability, guarantee the stabilization of above-mentioned lifetime of LED.
It is above-mentioned instruct thinking under, by the first metal oxide layer 11, graphene layer 12 contained by anode 10 and
Aspect optimizes two metal oxide layers 13 as follows, realizes the light extraction efficiency for optimizing anode 10 and electrical stability and machinery
The performances such as stability.
Therefore, in an embodiment, above-mentioned first metal oxide layer 11 and the second metal oxide layer 13 with a thickness of 5-
60nm.The thickness of two metal oxide layers 11 and 13 can be identical or not identical.In a particular embodiment, when first metal oxygen
When compound layer 11 is combined with the stacking of base layer 01, the preferred 15-60nm of the thickness of first metal oxide layer 11.In this thickness
When range, which can select glass substrate, due to glass substrate (n1=1.45) and 12 (n2=of graphene layer
2.72) refractive index is larger, at this time the refractive index of first metal oxide layer 11 should between n1 and n2, and first
The thickness of metal oxide layer 11 is preferably controlled between 15-60nm, on the one hand can more effectively protect graphene layer 12, is improved
The stability of 10 structure of anode；On the other hand, the refractive index between base layer 01 and graphene layer 12 is adjusted, anode 10 is improved
Optical property improves light emission rate.In another embodiment, control the second metal oxide layer 13 with a thickness of 10-40nm,
The thickness is matched with above-mentioned second metal oxide layer, 13 thickness, improves the protective effect to graphene layer 12, improves anode
10 structural stability and optical property improves light emission rate.
In another embodiment, graphene layer 12 with a thickness of 50-100nm.In another embodiment, above-mentioned anode 10 exists
It during preparation, that is to say in each layer of formation, anode 10 is made annealing treatment, and is specifically such as being sequentially depositing first
It after metal oxide layer 11 and graphene layer 12, is made annealing treatment, or further, is forming the second metal oxide
It is made annealing treatment again after layer 13.In a particular embodiment, the temperature of the annealing is 100-200 DEG C, specifically may be used
It, specifically can be with but not just for 15min with but not just for 150 DEG C, time 10-30min.By to each layer contained by anode 10
The thickness of structure further controls and optimizes formation condition, is not only able to improve the light extraction efficiency of anode 10, and
And protective effect of the metal oxide layer to graphene layer 12 can also be improved, and then improve the electrical stability and machine of anode 10
Tool stability.
On the basis of above-mentioned 10 each embodiment of anode, first metal oxide layer 11 and the second metal oxide layer
Identical or different metal oxide contained by 13 is MoO3、V2O5、TiO2、SnO2、NiO、WO3At least one of.The gold
The light extraction efficiency of anode 10 can not only be improved by belonging to oxide, and can be improved the stability of 10 structure of anode, but also
The ability of hole injection can be improved.
Above-mentioned luminescence unit 20 can be conventional luminescence unit.It is above-mentioned to shine in an embodiment in conjunction with above-mentioned anode 10
Unit 20 may include luminescent layer 23, can also include hole functional layer, luminescent layer 23 and the electric function for stacking gradually combination
Layer.
Wherein, hole functional layer may include hole injection layer 21, one layer or the knot that is stacked on one another in hole transmission layer 22
Two layers closed.It is that stacking is incorporated in anode 10 and shines when hole functional layer is hole injection layer 21 or hole transmission layer 22
Between layer 23；When hole functional layer is 22 composite layer of hole injection layer 21 and hole transmission layer, by anode 10 to luminescent layer 23
Direction, hole injection layer 21 and hole transmission layer 22 stack gradually, and that is to say that hole injection layer 21 is combined with the stacking of anode 10, empty
Cave transport layer 22 is combined with the stacking of luminescent layer 23.By adding hole functional layer, the hole at 10 end of anode can be effectively improved
It injects and is transmitted in luminescent layer 23, improve it with electronics and be compounded to form exciton amount, to improve the luminous efficiency of luminescent layer 23.
In addition, the metal oxide layer as contained by anode 10 is also improved the ability of hole injection, which can
To omit.In a particular embodiment, the thickness of hole injection layer 21 can be 50-100nm, and the material of hole injection layer 21 can be with
But not just in PEDOT:PSS, nickel oxide, molybdenum oxide, vanadium oxide, copper oxide, copper sulfide, copper rhodanide, cupric iodide extremely
Few one kind；The thickness of the hole transmission layer 22 can be 0-100nm, preferably 40-100nm, more excellent 40-50nm.Hole passes
The material of defeated layer 22 can be with but not just at least one of TFB, PVK, Poly-TPD, TCTA, CBP；The luminescent layer 23
Thickness can be 10-100nm, preferably 20-40nm, the material of luminescent layer 23 is quantum dot light emitting material or organic light emission material
Material.Wherein, when the material of luminescent layer 23 is quantum dot light emitting material, above-mentioned light emitting diode is light emitting diode with quantum dots
(QLED), at this point, the material of luminescent layer 23 can be common red, green, blue and gold-tinted quantum dot and infrared and ultraviolet light quantity
Son point at least one of, specific quantum dot can for II-VI group compound, III-V compound, II-V compounds of group,
One in III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group or IV race simple substance
Kind is a variety of.When the material of luminescent layer 23 is luminous organic material, above-mentioned light emitting diode is Organic Light Emitting Diode
(OLED), at this point, luminous organic material can be conventional luminous organic material.
Electronic work ergosphere contained by above-mentioned luminescence unit 20 may include electron transfer layer 24, (figure is not shown electron injecting layer
Show) in one layer or two layers of the combination that is stacked on one another.It is layer when electronic work ergosphere is electron transfer layer 24 or electron injecting layer
It is folded to combine between luminescent layer 23 and cathode 30；When the composite layer that electronic work ergosphere is electron transfer layer 24 and electron injecting layer
When, by luminescent layer 23 to 30 direction of cathode, electron transfer layer 24 and electron injecting layer are stacked gradually, and that is to say electron transfer layer 24
It is combined with the stacking of luminescent layer 23, electron injecting layer is combined with the stacking of cathode 30.By adding electronic work ergosphere, can effectively improve
It the injection of the electronics at 30 end of cathode and is transmitted in luminescent layer 23, improves it and hole-recombination forms exciton amount, to improve hair
The luminous efficiency of photosphere 23.In a particular embodiment, the thickness of electron transfer layer 24 can be 10-100nm, electron transfer layer 24
Material can be ZnO, TiO2、Ca、Ba、ZrO2、CsF、LiF、CsCO3、Alq3At least one of；The electron injecting layer
Thickness can be 30-100nm, preferably 30-60nm, the material of electron injecting layer can be the common electronics of light emitting diode
Implanted layer.
Therefore, pass through the control to each functional layer structure contained by luminescence unit 20 and each functional layer thickness and material category
System and optimization can effectively improve the luminous efficiency of luminescence unit 20, and the light that the luminescence unit 20 issues can be by above-mentioned
Anode 10 improves light extraction efficiency.
Above-mentioned cathode 30 can be the cathode of conventional light emitting diode, and such as in one embodiment, for example metallic silver layer is negative
Pole or aluminum metal cathode.The thickness of cathode 30 can be conventional thickness, for example but not just for 100nm.
In addition, the first metal oxide layer 11 and the second metal contained by each embodiment light emitting diode shown in above-mentioned Fig. 1
The position of oxide skin(coating) 13 can be interchanged.
In another embodiment, when cathode 30 is as light-emitting surface, 30 structure of cathode is as shown in Figure 2.Anode 10 can be hair
Optical diode conventional anodes, luminescence unit 20 can be luminescence unit 20 described in Fig. 1, in order to save length, herein no longer
It repeats.30 structure of cathode is as shown in Figure 2 comprising stacks gradually the first metal oxide layer 31,32 and of graphene layer of combination
Second metal oxide layer 33, the first metal oxide layer 31 or the second metal oxide layer 33 and electricity contained by luminescence unit 20
Subfunction layer stackup combines, and can specifically be combined with electron injecting layer or the stacking of electron transfer layer 24.Wherein, the first metal aoxidizes
Nitride layer 31,33 structure feature of the second metal oxide layer and material the first metal oxide layer as described in figure 1 above
11, the second metal oxide layer, 13, the graphene layer 12 as described in figure 1 above of graphene layer 32.Therefore, in order to save
Length, the structure feature of details are not described herein the first metal oxide layer 31, graphene layer 32 and the second metal oxide layer 33
And material property.
In addition, the first metal oxide layer 31 and the second metal contained by each embodiment light emitting diode shown in above-mentioned Fig. 2
The position of oxide skin(coating) 33 can be interchanged.
Based on above-mentioned light emitting diode as shown in Figure 1 or 2, it can make just to set structure and be also possible to inverted structure.
Therefore, above-mentioned light emitting diode can effectively improve light emitting diode by contained interlayer composite anode 10 or cathode 30
Light extraction efficiency, and then increase photoelectric efficiency, and improve light emitting diode electrical stability and mechanical stability, guarantee above-mentioned
The stabilization of lifetime of LED.In addition, by adjustment and optimization to contained 20 functional layer structure of luminescence unit, Neng Gouyou
The luminous efficiency that effect improves above-mentioned light emitting diode improves above-mentioned light emitting diode under the action of anode 10 or cathode 30
Light emission rate.
(2) preparation method of light emitting diode
On the other hand, on the basis of light emitting diode described above, the embodiment of the invention also provides above luminous two
The preparation method of pole pipe.In conjunction with Fig. 1,2, the preparation method of light emitting diode above can be prepared as follows:
One embodiment includes the following steps: when light emitting diode construction is as shown in Figure 1
Step S01. is in 01 surface deposition interlayer composite anode 10 of base layer: depositing the first metal oxygen on 01 surface of base layer
Compound layer 11, graphene layer 12 deposit the second metal oxide layer 13 on 12 surface of graphene layer after annealing；
Step S02. is sequentially prepared luminescence unit 20 and cathode 30 in 10 outer surface of anode: second metal oxide layer
Surface, which is sequentially depositing, prepares luminescence unit layer structure and cathode.
Specifically, the first metal oxide layer 11, graphene layer 12 and the second gold medal that the deposition in above-mentioned steps S01 is formed
The type of the thickness and material that belong to oxide skin(coating) 13 is as described above, in order to solve length, is not repeating herein.
Wherein, base layer 01 can be the common matrix of light emitting diode, such as glass.Before deposition forms anode 10,
The cleaning treatment on surface is preferably carried out to base layer 01, such as in a particular embodiment, such as glass substrate of base layer 01 is in order
It is placed in acetone, washing lotion is cleaned by ultrasonic in deionized water and isopropanol, and each of the above step ultrasound is both needed to lasting 15 minutes left sides
It is right.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound.
Deposited on 01 surface of base layer the first metal oxide layer 11 method can with but not only using vapor deposition.
Deposited on 11 surface of the first metal oxide layer graphene layer 12 method can with but not just for chemical method or
Physical method deposition.Wherein, chemical method deposition includes: chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodic oxidation
Method, strike, coprecipitation.Physical method deposition includes physical coating method or solwution method, and physical coating method includes: thermal evaporation
Coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition
Method, pulsed laser deposition.Solwution method includes: spin-coating method, print process, knife coating, dip-coating method, infusion method, spray coating method, rolling
Coating, casting method, slit coating method, strip rubbing method.
After graphene layer 12 to be deposited, to be deposited with the base layer 01 of the first metal oxide layer 11 and graphene layer 12 into
Row annealing.In one embodiment, the temperature of annealing is 100-200, specific such as 150 DEG C, annealing time 10-
30min, it is specific such as 15min.
The method that the second metal oxide layer 13 is deposited on 12 surface of graphene layer can be such as the first metal oxide layer
11 deposition method is the same, is film-made using vapor deposition.
In addition, the sequence of the first metal oxide layer 11 of preparation and the second metal oxide layer 13 can be interchanged, such as first exist
01 surface of base layer on deposition preparation the second metal oxide layer 13, be then sequentially prepared graphene 12 and the first metal oxidation
Nitride layer 11.
20 layers of structure of luminescence unit and cathode 30 are prepared in above-mentioned steps S02 can conventionally be made
It is standby.In order to improve luminous efficiency and improve above-mentioned light emitting diode, 20 layers of structure of the luminescence unit are prepared as follows:
According to layer structure contained by luminescence unit 20 described above, successively in the appearance wheat flour of the second metal oxide layer 13
Standby each layer structure, such as when luminescence unit 20 containing hole injection layer 21, hole transmission layer 22, luminescent layer 23, electron transfer layer 24,
When the layers structure such as electron injecting layer, in 13 outer surface of the second metal oxide layer successively each layer structure.Certainly, such as luminescence unit 20
When containing only hole injection layer 21, any layer in hole transmission layer 22, prepared in the outer surface of the second metal oxide layer 13
Luminescent layer 23 is prepared after any layer in hole injection layer 21, hole transmission layer 22.As luminescence unit 20 contains only electron-transport
When layer 24, any layer in electron injecting layer, any in the outer surface electron transfer layer 24, electron injecting layer of luminescent layer 23
Layer.
In addition, preparing hole injection layer 21, hole transport to further increase the quality of each layer and chemical property
It after layer 22, electron transfer layer 24, each layer of electron injecting layer, is made annealing treatment, after such as preparing hole injection layer 21, is carried out respectively
Annealing, after preparing hole transmission layer 22, is made annealing treatment again, it is latter to prepare electron transfer layer 24, electron injecting layer 2
Sample is made annealing treatment respectively.Wherein, preparing luminescent layer 23 can be without annealing.In one embodiment, annealing
Temperature is 100-200, specific such as 150 DEG C, annealing time 10-30min, specific such as 15min.In addition, preparing electronics
After functional layer such as electron transfer layer 24, it can be placed on 60-100 DEG C of warm table and heat 20-40 minutes, remove remaining molten
Agent.
The method of deposition cathode 30 can be conventional method, as prepared by vapour deposition method.
In addition, the type of the thickness and material of 20 each layers of structure of the luminescence unit prepared in step S02 and cathode 30 is such as
Described in light emitting diode above, in order to solve length, do not repeating herein.
Therefore, above-mentioned light emitting diode is using sedimentation so as to form 11/ graphene layer 12/ of the first metal oxide layer the
The sandwich composite anode 10 of two metal oxide layers 13 ensure that anode 10 so that 10 structural behaviour of anode is stablized
Synergistic effect between contained metal oxide layer (11,13) and graphene layer 12, specifically ensure that metal oxide with
The micro-optics microcavity that graphene is formed plays microcavity resonance effects, improves the light extraction efficiency of light emitting diode, while
The electrical stability and mechanical stability of anode 10 has been effectively ensured.In addition, above-mentioned preparation method process conditions are easily-controllable, ensure that
The electrical stability and mechanical stability of the light emitting diode of preparation.
Another embodiment can be according to above-described embodiment preparation method point when light emitting diode construction is as shown in Figure 2
It is not sequentially prepared each layer structure according to LED layers structure shown in Fig. 2 on 01 surface of base layer, is a difference in that
Luminescence unit prepares cathode 30 on 20 surface, and the first metal oxide layer 31, stone are specifically prepared on 20 surface of luminescence unit
Black alkene layer 32 and the second metal oxide layer 33.The method for preparing the first metal oxide layer 31 and the second metal oxide layer 33
Such as the method for the first metal oxide layer 11 of preparation or the second metal oxide layer 13, the method for preparing graphene layer 32 can be with
Method as prepared graphene layer 12 does not repeat the preparation method of cathode 30 herein in order to save length.Therefore,
Above-mentioned light emitting diode is using sedimentation so as to form 31/ graphene layer of the first metal oxide layer, 32/ second metal oxide
The sandwich composite cathode 30 of layer 33 ensure that metal oxygen contained by cathode 30 so that 30 structural behaviour of cathode is stablized
Synergistic effect between compound layer (31,33) and graphene layer 32 specifically ensure that metal oxide and graphene were formed
Micro-optics microcavity plays microcavity resonance effects, improves the light extraction efficiency of light emitting diode, while yin has also been effectively ensured
The electrical stability and mechanical stability of pole 30.In addition, above-mentioned preparation method process conditions are easily-controllable, it ensure that luminous the two of preparation
The electrical stability and mechanical stability of pole pipe.
(3) application of light emitting diode
There is high light extraction efficiency and luminous efficiency based on light emitting diode described above.Therefore, hair described above
Optical diode can be applied to display device or solid-state lighting lamp field, to improve display or the hair of corresponding device
Optical property.The embodiment of the present invention is on the basis of light emitting diode above as a result, provides a kind of display device or solid-state lighting
Lamps and lanterns.Wherein, display device or solid-state lighting lamp are respectively provided with its corresponding necessary component, include in necessary component
Light emitting diode described above.In this way, its of display screen of the embodiment of the present invention or solid-state lighting lamp it is luminous loss it is small, out
Light rate is high, and uses stable working performance, long service life.
Now in conjunction with specific example, the present invention will be described in further detail.Wherein, the hereafter "/" table in each embodiment
What is shown is the meaning that stacking combines.
Embodiment 1
The present embodiment composite anode light emitting diode comprising structure is as shown in Figure 1, include the glass for stacking gradually combination
Glass/MoO3(20nm)/graphene (80nm)/MoO3(20nm)/PEDOT:PSS (40nm)/TFB (50nm)/quantum dot light emitting layer
(70nm)/ZnO(40nm)/Al(100nm)。
The present embodiment light emitting diode is prepared as follows:
S11: being placed in acetone for glass substrate 0 in order, washing lotion, is cleaned by ultrasonic in deionized water and isopropanol,
Each of the above step ultrasound is both needed to lasting 15 minutes or so.It is dried for standby after which substrate is placed in cleaning oven after the completion of ultrasound；
S12: after substrate is dry, one layer of MoO is deposited on it3Then metal oxide 11 deposits one layer of stone on it
Black alkene layer 12, after place it on 150 DEG C of warm table and heat 15min, after aforesaid substrate include after graphene layer is cooling, in stone
One layer of same MoO of redeposition on black alkene layer3Metal oxide 13 forms anode 10.
S13: depositing PEDOT:PSS hole injection layer 21 on 10 surface of anode, after in 150 DEG C of annealing 15min, it is to be cooled
Afterwards, on 21 surface of hole injection layer deposit TFB hole transmission layer 22, after in 150 DEG C of annealing 15min；After cooling, in hole
Depositing light emitting layer 23 on 22 surface of transport layer does not heat the deposition ZnO electron transfer layer 24 directly on 23 surface of luminescent layer, deposition
Piece is placed on after the completion on 80 DEG C of warm table and is heated 30 minutes, remove remaining solvent, preparation forms luminescence unit 20；
S14: piece for having deposited each functional layer that step S14 is handled is placed in vapor deposition storehouse through mask plate hot evaporation one
The metal Al of layer 100nm is cathode, is tested after encapsulation spare.
Embodiment 2
The present embodiment composite anode light emitting diode comprising structure is as shown in Figure 1, include the glass for stacking gradually combination
Glass/MoO3(50nm)/graphene (50nm)/WO3(10nm)/TFB (80nm)/quantum dot light emitting layer (40nm)/ZnO (40nm)/Al
(100nm)。
The present embodiment light emitting diode is as follows referring to the preparation method of embodiment 1.
Embodiment 3
The present embodiment composite anode light emitting diode comprising structure is as shown in Figure 1, include the glass for stacking gradually combination
Glass/TiO2(50nm)/graphene (50nm)/V2O5(10nm)/TFB (80nm)/quantum dot light emitting layer (40nm)/ZnO (40nm)/
Al(100nm)。
The present embodiment light emitting diode is as follows referring to the preparation method of embodiment 1.
Embodiment 4
The present embodiment composite anode light emitting diode comprising structure is as shown in Figure 1, include the glass for stacking gradually combination
Glass/TiO2(20nm)/graphene (80nm)/TiO2(20nm)/PEDOT:PSS (40nm)/TFB (50nm)/quantum dot light emitting layer
(70nm)/ZnO(40nm)/Al(100nm)。
The present embodiment light emitting diode is as follows referring to the preparation method of embodiment 1.
Embodiment 5
The present embodiment composite anode light emitting diode comprising structure is as shown in Figure 1, include the glass for stacking gradually combination
Glass/NiO (20nm)/graphene (80nm)/NiO (20nm)/PEDOT:PSS (40nm)/TFB (50nm)/quantum dot light emitting layer
(70nm)/ZnO(40nm)/Al(100nm)。
Embodiment 6
The present embodiment is inverted composite anode light emitting diode comprising stacks gradually glass/Al (100nm)/ZnO of combination
(40nm)/quantum dot light emitting layer (70nm)/TFB (50nm)/PEDOT:PSS (40nm)/NiO (20nm)/graphene (80nm)/
NiO(20nm)。
Embodiment 7
The present embodiment composite cathode light emitting diode comprising stack gradually electro-conductive glass/ITO (100nm) of combination/
PEDOT:PSS (40nm)/TFB (50nm)/quantum dot light emitting layer (70nm)/ZnO (40nm)/NiO (20nm)/graphene
(80nm)/NiO(20nm)。
Embodiment 8
The present embodiment is inverted composite cathode light emitting diode comprising stacks gradually glass/NiO (20nm)/stone of combination
Black alkene (80nm)/NiO (20nm)/ZnO (40nm)/quantum dot light emitting layer (70nm)/TFB (50nm)/PEDOT:PSS (40nm)/
ITO(100nm)。
Embodiment 9
The present embodiment composite anode light emitting diode comprising stack gradually glass/NiO (20nm)/graphene of combination
(80nm)/NiO (20nm)/quantum dot light emitting layer (70nm)/Al (100nm).
Embodiment 10
The present embodiment is inverted composite anode light emitting diode comprising stacks gradually glass/Al (100nm)/amount of combination
Son point luminescent layer (70nm)/NiO (20nm)/graphene (80nm)/NiO (20nm).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of light emitting diode comprising anode and cathode and the luminescence unit being incorporated between the anode and cathode,
It is characterized by: the anode or cathode includes the first metal oxide layer, graphene layer and the second gold medal for stacking gradually combination
Belong to oxide skin(coating), and first metal oxide layer or the second metal oxide layer are combined with luminescence unit stacking.
2. light emitting diode according to claim 1, it is characterised in that: the thickness 15- of first metal oxide layer
60nm；
Second metal oxide layer with a thickness of 10-40nm；And/or
The graphene layer with a thickness of 50-100nm.
3. light emitting diode according to claim 1, it is characterised in that: the anode at least through primary annealing at
Reason, the temperature of the annealing are 100-200 DEG C, time 10-30min.
4. light emitting diode according to claim 1 to 3, it is characterised in that: first metal oxide layer and
Identical or different metal oxide contained by two metal oxide layers is MoO3、V2O5、TiO2、SnO2、NiO、WO3In extremely
Few one kind.
5. light emitting diode according to claim 1 to 3, it is characterised in that: the luminescence unit includes stacking gradually
In conjunction with hole functional layer, luminescent layer and electronic work ergosphere；Wherein,
The hole functional layer includes that hole injection layer, the sky in conjunction with the luminous layer stackup combined is laminated with the anode
Two layers of one layer in the transport layer of cave or the combination that is stacked on one another；And/or
The electronic work ergosphere includes that electron injecting layer, the electricity in conjunction with the luminous layer stackup combined is laminated with the cathode
Two layers of one layer in sub- transport layer or the combination that is stacked on one another.
6. light emitting diode according to claim 5, it is characterised in that: the hole injection layer with a thickness of 50-
100nm,
The hole transmission layer with a thickness of 40-100nm；
The luminescent layer with a thickness of 10-100nm；
The electron injecting layer with a thickness of 30-100nm；
The electron transfer layer with a thickness of 10-100nm.
7. light emitting diode according to claim 5 or 6, it is characterised in that: the material of the hole injection layer is
At least one of PEDOT:PSS, nickel oxide, molybdenum oxide, vanadium oxide, copper oxide, copper sulfide, copper rhodanide, cupric iodide；
The material of the hole transmission layer is at least one of TFB, PVK, Poly-TPD, TCTA, CBP；
The material of the luminescent layer is quantum dot light emitting material or luminous organic material；
The material of the electron transfer layer is ZnO, TiO2、Ca、Ba、ZrO2、CsF、LiF、CsCO3、Alq3At least one of.
8. the preparation method of the light emitting diode as described in claim 1-4 is any, which is characterized in that including preparing anode as follows
Or the step of cathode:
It is sequentially depositing the first metal oxide layer, graphene layer in matrix layer surface or luminescence unit surface, by annealing
The second metal oxide layer is deposited on the graphene layer surface afterwards；Or
It is sequentially depositing the second metal oxide layer, graphene layer in matrix layer surface or luminescence unit surface, by annealing
The first metal oxide layer is deposited on the graphene layer surface afterwards.
9. preparation method according to claim 8, it is characterised in that: the temperature of the annealing is 100-200 DEG C, when
Between be 10-30min.
10. a kind of display device or solid-state lighting lamp, it is characterised in that: the display device or solid-state lighting lamp are containing having the right
Benefit requires any light emitting diode of 1-7 or the light emitting diode by any preparation method preparation of claim 8-9.
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