CN110277502A - Light emitting diode with quantum dots and preparation method thereof - Google Patents
Light emitting diode with quantum dots and preparation method thereof Download PDFInfo
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- CN110277502A CN110277502A CN201810208473.9A CN201810208473A CN110277502A CN 110277502 A CN110277502 A CN 110277502A CN 201810208473 A CN201810208473 A CN 201810208473A CN 110277502 A CN110277502 A CN 110277502A
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- light emitting
- emitting diode
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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
- H10K50/813—Anodes characterised by their shape
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
Abstract
The invention belongs to technology of quantum dots fields, and in particular to a kind of light emitting diode with quantum dots and preparation method thereof.The light emitting diode with quantum dots, including hearth electrode and top electrode, and the quantum dot light emitting layer being arranged between the hearth electrode and the top electrode, it is characterised in that, the hearth electrode surface opposite with the quantum dot light emitting layer is in pleated structure, and the hearth electrode is made of metal material.Light emitting diode with quantum dots of the invention can effectively reduce SPP loss, improve device light extraction efficiency by the pleated structure being arranged on the surface of hearth electrode (can be cathode, be also possible to anode).
Description
Technical field
The invention belongs to quantum dot fields, and in particular to a kind of light emitting diode with quantum dots and preparation method thereof.
Background technique
Quantum dot light emitting device is to add the device that direct voltage drive quanta point material shines, tool in anode and cathode
Colored saturation, purity is high, monochromaticjty is good, Color tunable and the advantages that can be prepared with solwution method, it is considered to be the next generation is flat
The advantage technology of plate display.
Due to the multilayered structure of light emitting diode with quantum dots, photon in luminescence process be radiated device exterior can be with not
Most energy is lost with form, to weaken the external quantum efficiency of device.The form of its energy loss includes: metal watch
Surface plasma excimer (SPP) loss, substrate waveguide mode, ITO/ organic layer waveguide mode etc., wherein SPP loss is larger.SPP
It is a kind of mixed activation state formed that interacted by free electron and photon of local on medium/metal interface, is a kind of
The guided wave mode that can only be propagated along interface direction, and the energy of final SPP all translates into Joule heat and loses, and leads to device amount
Sub- inefficiency.All there is SPP loss in bottom emitting and top emitting light emitting diode with quantum dots, wherein in top emitting device
SPP loss is more serious, because usually all using metal electrode in cathode, anode in the device of top emitting, and two metal electrodes
There will be SPP loss, how reduce SPP loss, be of great significance for the commercial applications of light emitting diode with quantum dots.
Therefore, many researchers attempt to take different means to reduce SPP loss, for example increase between luminescent layer and metal electrode
Distance, since SPP is to be radiated to cause with metal interaction by exciton in light emitting diode with quantum dots, although can subtract in this way
Few SPP loss, but also will increase device operating voltages, while increasing waveguide mode loss.
Therefore, the prior art has much room for improvement.
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 with quantum dots and its system are provided
Preparation Method, it is intended to solve all there is technical issues that SPP in existing light emitting diode with quantum dots.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of light emitting diode with quantum dots, including hearth electrode and top electrode, and is arranged in institute
State the quantum dot light emitting layer between hearth electrode and the top electrode, the hearth electrode surface opposite with the quantum dot light emitting layer
In pleated structure, and the hearth electrode is made of metal material.
Another aspect of the present invention provides a kind of preparation method of light emitting diode with quantum dots, includes the following steps:
Substrate is provided；
On the substrate by metal material deposition, it is then made annealing treatment, obtains surface is in pleated structure first
Metal electrode layer；The metal material is deposited on first metal electrode layer again, obtains the second metal electrode layer；Its
In, first metal electrode layer and second metal electrode layer form the hearth electrode.
Quantum dot light emitting layer is deposited on second metal electrode layer, the deposition top electricity on the quantum dot light emitting layer
Pole.
Light emitting diode with quantum dots provided by the invention, by hearth electrode (can be cathode, be also possible to anode)
The pleated structure of surface setting can effectively reduce SPP loss, improve device light extraction efficiency.SPP is a kind of free electron and photon
Interact the guided wave mode formed, when SPP wave vector, which is less than, is emitted light wave vector in luminescent layer, SPP mode wave vector energy
Photon radiation is converted into be extracted, and the electrode of pleated structure can make SPP wave generate the loss of momentum by random scatter,
The transformation efficiency of SPP to light radiation is improved, SPP loss is reduced.
In the preparation method of light emitting diode with quantum dots provided by the invention, the metal material for preparing electrode is deposited on base
On bottom, detailed process is: first depositing the first metal electrode layer, two-dimensional metallic film (i.e. the first metal electricity being deposited in substrate
Pole layer) it can be in thermodynamic instability state, metal material can occur irregularly to reunite, similar to " dewetting " in welding,
Heat treatment can accelerate this irregular reunion situation；After deposited the first metal electrode layer in substrate, high temperature rapid thermal annealing,
Make metal that irregular reunion occur, to form pleated structure, the second metal electrode is then deposited on the first metal electrode layer
Layer obtains the complete hearth electrode with pleated structure.The pleated structure electrode that the preparation method obtains can effectively reduce SPP damage
Consumption improves light emitting diode with quantum dots efficiency, and the method is easy to operate, is not necessarily to complicated technology, at low cost, is suitable for big ruler
Very little industrial production.
Detailed description of the invention
Fig. 1 is hearth electrode of embodiment of the present invention preparation process schematic diagram.
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.
On the one hand, the embodiment of the invention provides a kind of light emitting diode with quantum dots, including hearth electrode and top electrode, and
Quantum dot light emitting layer between the hearth electrode and the top electrode, the hearth electrode and the quantum dot light emitting layer phase are set
Pair surface be in pleated structure, and the hearth electrode is made of metal material.
Light emitting diode with quantum dots provided in an embodiment of the present invention, by (can be cathode in hearth electrode, being also possible to sun
Pole, when the hearth electrode is anode, the top electrode is cathode；When the hearth electrode is cathode, the top electrode is sun
Pole) surface setting pleated structure, can effectively reduce SPP loss, improve device light extraction efficiency.SPP is a kind of free electron
Interact the guided wave mode to be formed with photon, when SPP wave vector, which is less than, is emitted light wave vector in luminescent layer, SPP mode wave
Vector can be converted into photon radiation and be extracted, and the electrode of pleated structure can make SPP wave generate momentum by random scatter
Loss improves the transformation efficiency of SPP to light radiation, reduces SPP loss.
Further, the hearth electrode with a thickness of 45-260nm.Further, when the light emitting diode with quantum dots
When for bottom emitting type light emitting diode with quantum dots, the thickness of hearth electrode is preferably 45-85nm, when the light emitting diode with quantum dots
When for top emission type light emitting diode with quantum dots, the thickness of hearth electrode is preferably 100-260nm.It, can specifically when preparation
It first metal material to be deposited in substrate, then makes annealing treatment, obtains with a thickness of 30-60nm, surface in the of pleated structure
One metal electrode layer, the second metal that then deposition thickness is 15-25nm or 70-200nm on first metal electrode layer
Electrode layer.
The principle of hearth electrode thickness selection are as follows: the thickness of the first metal electrode layer first deposited may be selected in 30-60nm, such as
The too small metal film of fruit thickness can not generate the biggish pleated structure of surface undulation, can not play the role of effective random scatter to subtract
Few SPP loss；And blocked up film can make metallic film tend to thermodynamic stability, it is difficult to occur during heat treatment not
Rule agglomerates into pleated structure.Because the first metal electrode layer is with a thickness of 30-60nm, and there is pleated structure, is hardly formed
Electrode layer with complete function, so can redeposited the second metal electricity with a thickness of 15-25nm on the first metal electrode layer
Pole layer, to form the complete hearth electrode with a thickness of 45-85nm, hearth electrode in this case is relatively thin, may adapt to
Bottom emitting type light emitting diode with quantum dots.
However, making deposition film be easy to hold in this way in island growth due to the presence of the first metal electrode layer pleated structure
Easily there are electrode hole, electrode hole will cause the generation of blackspot in device light emitting region, while also will increase the leakage in device
Electric current.In order to eliminate electrode hole this problem, the embodiment of the present invention is made to generate better effect, it can be in the first metal electrode layer
Upper preferred deposition with a thickness of 70-200nm the second metal electrode layer.If the second metal electrode layer of deposition is excessively thin can also
There are holes；Deposit the second blocked up metal electrode layer and will cause entire thickness of detector and increase, at the same increase time and technique at
This.The complete hearth electrode obtained after the second metal electrode layer that deposition thickness is 70-200nm with a thickness of 100-260nm, because of this
In the case of hearth electrode due to blocked up, be not suitable for bottom emitting type light emitting diode with quantum dots, be suitable only for top emission type amount
Sub- point luminescent diode.Hearth electrode under the thickness can not only reduce SPP loss, but also can eliminate electrode hole, because
This, in the embodiment of the present invention, the effect of top emission type light emitting diode with quantum dots is optimal.
Further, the metal material includes at least one of Al, Ag and Cu/Pt alloy.
Further, such as hearth electrode is anode, and the top electrode is cathode；Then the anode and the quantum dot are sent out
Hole injection layer and hole transmission layer are also stacked between photosphere, the hole injection layer is adjacent with the anode；And institute
It states and has also been stacked electron injecting layer and electron transfer layer between cathode and the quantum dot light emitting layer, the electron injecting layer
It is adjacent with the cathode.If the hearth electrode is cathode, the top electrode is anode, also can be such.
Further, the light emitting diode with quantum dots is top emission type light emitting diode with quantum dots or bottom emitting type quantum
Point luminescent diode.Because all there is SPP loss in the light emitting diode with quantum dots of bottom emitting type and top emission type, so the two
It is all suitable for.However, the SPP loss in the device of top emission type is more serious, because usually in cathode, sun in the device of top emission type
Pole all uses metal electrode, and two metal electrodes can all have SPP loss, therefore the light emitting diode with quantum dots of the present embodiment
Preferably top emission type light emitting diode with quantum dots.But as stated above, for example two pole of bottom emitting type quantum dot light emitting
Pipe, hearth electrode with a thickness of 50-80nm；For example top emission type light emitting diode with quantum dots, hearth electrode with a thickness of 100-
260nm。
On the other hand, the embodiment of the invention also provides a kind of preparation method of light emitting diode with quantum dots, including it is as follows
Step:
S01: substrate is provided；
S02: on the substrate by metal material deposition, then being made annealing treatment, and obtains surface in pleated structure
First metal electrode layer；The metal material is deposited on first metal electrode layer again, obtains the second metal electrode layer；
Wherein, first metal electrode layer and second metal electrode layer form the hearth electrode.
S03: depositing quantum dot light emitting layer on second metal electrode layer, and top is deposited on the quantum dot light emitting layer
Electrode.
Above-mentioned preparation method obtains in light emitting diode with quantum dots, and the hearth electrode is anode, and the top electrode is cathode；
Or the hearth electrode is cathode, the top electrode is anode.
In the preparation method of light emitting diode with quantum dots provided in an embodiment of the present invention, the metal material for preparing electrode is sunk
In substrate, detailed process is product: first depositing the first metal electrode layer, the two-dimensional metallic film (i.e. first being deposited in substrate
Metal electrode layer) it can be in thermodynamic instability state, metal material can occur irregularly to reunite, similar to " anti-in welding
Wetting ", heat treatment can accelerate this irregular reunion situation；After deposited the first metal electrode layer in substrate, high temperature is fast
Fast annealing makes metal that irregular reunion occur, to form pleated structure, the second gold medal is then deposited on the first metal electrode layer
Belong to electrode layer, obtains the complete hearth electrode with pleated structure.The pleated structure electrode that the preparation method obtains can effectively subtract
Few SPP loss, improves light emitting diode with quantum dots efficiency, and the method is easy to operate, is not necessarily to complicated technology, at low cost, fits
For large scale industrial production.
Further, in above-mentioned steps S01, the preferred glass substrate of substrate.
Further, in above-mentioned steps S02: the annealing carries out in inert gas.Inert gas can be nitrogen
Gas, helium, neon etc..Further, the temperature of the annealing is 500-80 DEG C；The time of the annealing is 2-
6min.Under conditions of the annealing, the hearth electrode that surface is in pleated structure can be preferably obtained.
Further, in above-mentioned steps S02, first metal electrode layer with a thickness of 30-60nm, when the quantum dot
Light emitting diode be bottom emitting type light emitting diode with quantum dots when, second metal electrode layer with a thickness of 15-25nm；Work as institute
State light emitting diode with quantum dots be top emission type light emitting diode with quantum dots when, second metal electrode layer with a thickness of 70-
200nm.Selection and deposition process about hearth electrode thickness have been explained above, and no longer illustrate here.In addition, the present invention is real
The metal material for applying example includes at least one of Al, Ag and Cu/Pt alloy.
The present invention successively carried out test of many times, and it is further detailed as reference pair invention progress now to lift A partial experiment result
Thin description, is described in detail combined with specific embodiments below.
Embodiment 1
A kind of preparation method of light emitting diode with quantum dots, includes the following steps:
Deposit Ag metal film i.e. the first metal electrode layer of 30-60nm on the glass substrate using vacuum evaporation technology (such as
Metal film 1 in Fig. 1).Utilize rta technique in 500-800 under nitrogen protection post-depositional first metal electrode layer
DEG C annealing 2-6min, accelerates the agglomeration of metal film, forms the pleated structure such as Fig. 1, the Ag of 70-200nm is then deposited again
Metal film i.e. the second metal electrode layer (metal film 2 as shown in figure 1), double layer of metal film (i.e. the first metal electrode layer and the second gold medal
Belong to electrode layer) it is used as device cathodes；Be sequentially depositing on cathode later device other luminous layer structures (such as quantum dot light emitting layer and
Anode).
Embodiment 2
A kind of preparation method of light emitting diode with quantum dots, includes the following steps:
Deposit Al metal film i.e. the first metal electrode layer of 30-60nm on the glass substrate using vacuum evaporation technology (such as
Metal film 1 in Fig. 1).Utilize rta technique in 500-800 under nitrogen protection post-depositional first metal electrode layer
DEG C annealing 2-6min, accelerates the agglomeration of metal film, forms the pleated structure such as Fig. 1, the Ag of 70-200nm is then deposited again
Metal film i.e. the second metal electrode layer (metal film 2 as shown in figure 1), double layer of metal film (i.e. the first metal electrode layer and the second gold medal
Belong to electrode layer) it is used as device cathodes；Be sequentially depositing on cathode later device other luminous layer structures (such as quantum dot light emitting layer and
Anode).
Embodiment 3
A kind of preparation method of light emitting diode with quantum dots, includes the following steps:
Deposit Cu/Pt metal film i.e. the first metal electrode layer of 30-60nm on the glass substrate using vacuum evaporation technology
(metal film 1 as shown in figure 1).Utilize rta technique in 500- under nitrogen protection post-depositional first metal electrode layer
800 DEG C of annealing 2-6min accelerate the agglomeration of metal film, form the pleated structure such as Fig. 1, are then deposited 70-200nm's again
Cu/Pt metal film i.e. the second metal electrode layer (metal film 2 as shown in figure 1), double layer of metal film (i.e. the first metal electrode layer and
Two metal electrode layers) device cathodes are used as, other luminous layer structure (such as quantum dot light emittings of device are sequentially depositing on cathode later
Layer and anode).
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 with quantum dots, including hearth electrode and top electrode, and setting is in the hearth electrode and top electricity
Quantum dot light emitting layer between pole, which is characterized in that the hearth electrode surface opposite with the quantum dot light emitting layer is in fold
Structure, and the hearth electrode is made of metal material.
2. light emitting diode with quantum dots as described in claim 1, which is characterized in that the hearth electrode with a thickness of 45-
260nm。
3. light emitting diode with quantum dots as described in claim 1, it is characterised in that the light emitting diode with quantum dots is top hair
Emitting light emitting diode with quantum dots or bottom emitting type light emitting diode with quantum dots.
4. light emitting diode with quantum dots as claimed in claim 3, which is characterized in that when the light emitting diode with quantum dots is bottom
When emission type light emitting diode with quantum dots, the hearth electrode with a thickness of 45-85nm；When the light emitting diode with quantum dots is top
When emission type light emitting diode with quantum dots, the hearth electrode with a thickness of 100-260nm.
5. light emitting diode with quantum dots as described in claim 1, which is characterized in that the metal material includes Al, Ag and Cu/
At least one of Pt alloy.
6. a kind of preparation method of light emitting diode with quantum dots, which comprises the steps of:
Substrate is provided；
On the substrate by metal material deposition, it is then made annealing treatment, obtains the first metal that surface is in pleated structure
Electrode layer；The metal material is deposited on first metal electrode layer again, obtains the second metal electrode layer；Wherein, institute
State the first metal electrode layer and second metal electrode layer composition hearth electrode.
Quantum dot light emitting layer is deposited on second metal electrode layer, deposits top electrode on the quantum dot light emitting layer.
7. the preparation method of light emitting diode with quantum dots as claimed in claim 6, which is characterized in that the annealing is lazy
It is carried out in property gas.
8. the preparation method of light emitting diode with quantum dots as claimed in claim 6, which is characterized in that the temperature of the annealing
Degree is 500-80 DEG C；And/or
The time of the annealing is 2-6min.
9. the preparation method of light emitting diode with quantum dots as claimed in claim 6, which is characterized in that first metal electrode
Layer with a thickness of 30-60nm, when the light emitting diode with quantum dots is bottom emitting type light emitting diode with quantum dots, described second
Metal electrode layer with a thickness of 15-25nm；When the light emitting diode with quantum dots is top emission type light emitting diode with quantum dots,
Second metal electrode layer with a thickness of 70-200nm.
10. the preparation method of light emitting diode with quantum dots as claimed in claim 6, which is characterized in that the metal material packet
Include at least one of Al, Ag and Cu/Pt alloy.
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Application publication date: 20190924 |