CN110504372A - 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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- CN110504372A CN110504372A CN201810466896.0A CN201810466896A CN110504372A CN 110504372 A CN110504372 A CN 110504372A CN 201810466896 A CN201810466896 A CN 201810466896A CN 110504372 A CN110504372 A CN 110504372A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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Abstract
The invention belongs to field of display technology, 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 cathode and anode, and the composite luminescence layer between the cathode and the anode is set, the composite luminescence layer includes at least one the quanta point material strip element and at least two ferrimagnet bar shaped units for being used to control Carrier composite being laid in the surface level of the cathode or the anode, and at least one described quanta point material strip element is located between two ferrimagnet bar shaped units.The light emitting diode with quantum dots can control the recombination region of carrier at composite luminescence layer center, to improve Carrier recombination rate, further increase the luminous efficiency of device.
Description
Technical field
The invention belongs to field of display technology, and in particular to a kind of light emitting diode with quantum dots and preparation method thereof.
Background technique
Light emitting diode with quantum dots (QLED) is to be become after exciton again based on hole and electronics quantum dot light emitting layer is compound
Radioluminescence, outer measure point efficiency (EQE) depend on coupling efficiency, spin state luminous efficiency, carrier balance rate etc..In reality
In the QLED luminescent device on border, since carrier injects and transmits uneven, cause electrons and holes number in luminescent layer different
It causes, and the transmission speed of the two is inconsistent, so that carrier be caused to assemble and shining between the interface of side, seriously reduces
Luminous efficiency.
Above-mentioned phenomenon is usually faced, one layer of carrier can be arranged between luminescent layer and carrier blocking layers and stop by people
Layer, for reducing leakage current and equilbrium carrier, makes it in luminescent layer uniformly light-emitting, rather than is gathered in side interface hair
Light.On the one hand method for increasing carrier barrier layer will increase carrier injection barrier, on the other hand also will increase technique
And cost, therefore seek the task of top priority of the more suitable method as equilbrium carrier.
It is well known that when carrier moves in magnetic field, it is fixed according to left hand if the direction of motion is vertical with magnetic direction
Then, carrier will receive the effect of Lorentz force, to deflect.It is exactly to utilize carrier in traditional magnetron sputtering
The effect for the Lorentz force being subject in toroidal magnetic field, by carrier control in the region close to magnetic field, to improve sputtering
Rate.
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 carrier mobility in existing light emitting diode with quantum dots it is too fast cause interface aggregates shine technology ask
Topic.
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 cathode and anode, and is arranged in the yin
Composite luminescence layer between pole and the anode, the composite luminescence layer include in the surface of the cathode or anode level
What is be laid with is used to control at least one quanta point material strip element and at least two ferrimagnets of Carrier composite
Strip element, and at least one described quanta point material strip element be located at two ferrimagnet bar shaped units it
Between.
Another aspect of the present invention provides a kind of preparation method of light emitting diode with quantum dots, includes the following steps:
Ferrimagnet is provided, the ferrimagnet is deposited on cathode or anode, growing has bar paten
Ferromagnetic layer;
Quanta point material is deposited in the gap of the ferromagnetic layer with bar paten, obtains recombination luminescence
Layer;Wherein, the composite luminescence layer includes being used to control carrier what the surface level of the cathode or the anode was laid with
At least one quanta point material strip element of recombination region and at least two ferrimagnet bar shaped units, and at least one
The quanta point material strip element is located between two ferrimagnet bar shaped units.
In light emitting diode with quantum dots provided by the invention, composite luminescence layer includes at least one quantum of same level
Point material strip element and at least two ferrimagnet bar shaped units, and at least one described quanta point material bar shaped list
Member is located between two ferrimagnet bar shaped units, and a toroidal magnetic field is formd in such composite luminescence layer, when
After carrier enters composite luminescence layer, in the quanta point material strip element between two ferrimagnet bar shaped units
Electric field force collective effect of the carrier by Lorentz force and inside in magnetic field, makes the movement of carrier deflect, thus
Helical trajectory is formed, carrier is controlled in composite luminescence layer center at this time, by the way that the recombination region control of carrier exists
Carrier recombination rate can be improved in composite luminescence layer center, further increases the luminous efficiency of device.
The preparation method of light emitting diode with quantum dots provided by the invention, in same level between a cathode and an anode
At least one quanta point material strip element and at least two ferrimagnet bar shaped units are deposited, and described at least one
Quanta point material strip element is located between two ferrimagnet bar shaped units, to form composite luminescence layer;The system
Preparation Method is simple for process, and implementation is facilitated to operate, and final light emitting diode with quantum dots obtained can be by the recombination region of carrier
Domain controls at composite luminescence layer center, to improve Carrier recombination rate, further increases the luminous efficiency of device.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of light emitting diode with quantum dots provided by the invention;
Fig. 2 is the structural schematic diagram of composite luminescence layer in a kind of light emitting diode with quantum dots provided by the invention;
Fig. 3 is motion profile of the carrier in composite luminescence layer in a kind of light emitting diode with quantum dots provided by the invention
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 cathode and anode, and setting
Composite luminescence layer between the cathode and the anode, the composite luminescence layer include in the cathode or the anode
At least one quanta point material strip element and at least two iron for being used to control Carrier composite that surface level is laid with
Magnetic material bar shaped unit, and at least one described quanta point material strip element is located at two ferrimagnet bar shapeds
Between unit.
In light emitting diode with quantum dots provided in an embodiment of the present invention, composite luminescence layer includes at least the one of same level
A quanta point material strip element and at least two ferrimagnet bar shaped units, and at least one described quanta point material
Strip element is located between two ferrimagnet bar shaped units, and an annular magnetic is formd in such composite luminescence layer
, quanta point material bar shaped list after carrier enters composite luminescence layer, between two ferrimagnet bar shaped units
Electric field force collective effect of the carrier by Lorentz force and inside in magnetic field in member, occurs the movement of carrier inclined
Turn, to form helical trajectory, it is multiple that carrier is can be improved at composite luminescence layer center in the recombination region control of carrier at this time
Conjunction rate further increases the luminous efficiency of device.The light emitting diode with quantum dots improves luminous position, can reduce device
Part structure simplifies technique, is not necessarily to carrier barrier layer, device performance and stability can be improved.
Further, in the above-mentioned light emitting diode with quantum dots of the embodiment of the present invention, the composite luminescence layer includes N number of institute
State the quanta point material strip element and N+1 ferrimagnet bar shaped units, and the quanta point material strip element and
The ferrimagnet bar shaped units alternately setting;Wherein, N is the integer more than or equal to 1.I.e. composite luminescence layer includes same water
Plane, the N number of quanta point material strip element and N+1 ferrimagnet bar shaped unit that alternate, each quantum dot material
Strip element is expected between two neighboring ferrimagnet bar shaped unit, and as depicted in figs. 1 and 2, QD is Quantum in figure
The white portion that Dot, QD are directed toward is quanta point material strip element, and FM is Ferro magnetic Materials, and FM refers to
To grey parts be ferrimagnet bar shaped unit.As shown in figure 3, foring an annular in such composite luminescence layer
Magnetic field, after carrier enters composite luminescence layer, each quanta point material strip element carriers is by magnetic field
Lorentz force and internal electric field force collective effect, to make the movement of carrier deflect to form helical trajectory, at this time
Carrier is controlled in composite luminescence layer center, can more efficiently avoid the occurrence of that carrier mobility is too fast to lead to interface
The luminous problem of aggregation, the preferred composite luminescence layer design can preferably improve Carrier recombination rate, improve more significantly
The luminous efficiency of device, effect are best.
Further, in light emitting diode with quantum dots provided in an embodiment of the present invention, the N=7 or 8.
Further, the width ratio of the width of the ferrimagnet bar shaped unit and the quanta point material strip element
Greater than 1:1, and the width of the ferrimagnet bar shaped unit is not less than 30nm, the iron in the ferrimagnet bar shaped unit
The remanent magnetism of magnetic material is greater than 0.5T;Wherein, the ferrimagnet is permanent magnet material or non-permanent magnet material.Under this condition
Magnetic field strength and electric field force collective effect, can make carrier recombination region control at composite luminescence layer center, meet these
It is required that magnetic material can choose permanent-magnet materials or non-permanent-magnet materials;It is further preferred that the non-permanent magnet material
In ferrous metal simple substance, cobalt metal simple-substance, nickel metal simple-substance, ferrocobalt, iron-nickel alloy, cobalt-nickel alloy and iron cobalt nickel alloy
At least one, the permanent magnet material be selected from aluminium nickel system permanent-magnet alloy, iron cobalt chromium system permanent-magnet alloy, permanent-magnet ferrite, rare earth
At least one of material such as rare earth cobalt permanent magnets and Nd-Fe-B permanent magnet material, and permanent composite material.
Further, in light emitting diode with quantum dots provided in an embodiment of the present invention, the composite luminescence layer with a thickness of
20nm-60nm.When the thickness of composite luminescence layer, that is, ferrimagnet bar shaped unit thickness is larger, device Qi Liang electricity will cause
It presses larger, and then will lead to strip of ferromagnetic material when the thickness of composite luminescence layer, that is, ferrimagnet bar shaped unit thinner thickness
The magnetic field strength that shape unit is formed is weaker, has been difficult to be obviously improved to device performance.It is further preferred that the thickness of composite luminescence layer
Degree is that 30nm-40nm is best.
Further, in light emitting diode with quantum dots provided in an embodiment of the present invention, the ferrimagnet bar shaped unit
It is made of permanent magnet material.I.e. ferrimagnet bar shaped unit is directly by permanent magnet material, in this case, ferrimagnet bar shaped
The width of unit is without limitation;Preferably, the permanent magnet material is selected from aluminium nickel system permanent-magnet alloy, iron cobalt chromium system permanent-magnet alloy, forever
At least one in magnetic ferrites, rare earth material such as rare earth cobalt permanent magnets and Nd-Fe-B permanent magnet material, and permanent composite material
Kind.Further, in light emitting diode with quantum dots provided in an embodiment of the present invention, the remanent magnetism of the permanent magnet material is greater than
1.1T.Remanent magnetism is bigger, is more conducive to make permanent magnet material.
Further, in light emitting diode with quantum dots provided in an embodiment of the present invention, the composite luminescence layer and the sun
Sky acupoints layer has been stacked between pole.The hole functional layer is hole transmission layer, at least one layer in hole injection layer;
It i.e. can be successively from anode to composite luminescence layer are as follows: anode, hole transmission layer, composite luminescence layer, or injected for anode, hole
Layer, composite luminescence layer, or be anode, hole injection layer, hole transmission layer, composite luminescence layer.And the composite luminescence layer and institute
It states and has been stacked electronic work ergosphere between cathode.The electronic work ergosphere be electron transfer layer, in electron injecting layer at least
One layer;It i.e. can be successively from cathode to composite luminescence layer are as follows: cathode, electron transfer layer, composite luminescence layer, or be cathode, electronics
Implanted layer, composite luminescence layer, or be cathode, electron injecting layer, electron transfer layer, composite luminescence layer.
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: providing ferrimagnet, the ferrimagnet be deposited on cathode or anode, and growth has bar chart
The ferromagnetic layer of case;
S02: quanta point material is deposited in the gap of the ferromagnetic layer with bar paten, is obtained compound
Luminescent layer;Wherein, the composite luminescence layer includes carrying what the surface level of the cathode or the anode was laid with for controlling
At least one quanta point material strip element and at least two ferrimagnet bar shaped units of sub- recombination region are flowed, and at least
One quanta point material strip element is located between two ferrimagnet bar shaped units.
The preparation method of light emitting diode with quantum dots provided in an embodiment of the present invention, same water between a cathode and an anode
At least one quanta point material strip element and at least two ferrimagnet bar shaped units, and at least one are deposited in plane
A quanta point material strip element is located between two ferrimagnet bar shaped units, to form recombination luminescence
Layer;The preparation method is simple for process, and implementation is facilitated to operate, and final light emitting diode with quantum dots obtained can be by carrier
Recombination region controls at composite luminescence layer center, to improve Carrier recombination rate, further increases the luminous effect of device
Rate.
Further, in above-mentioned preparation method, the composite luminescence layer include N number of quanta point material strip element and
The N+1 ferrimagnet bar shaped units, and the quanta point material strip element and the ferrimagnet bar shaped unit
It is arranged alternately;Wherein, N is the integer more than or equal to 1.The N number of quanta point material strip element being arranged alternately with each other and N+1 iron
Magnetic material bar shaped unit, that is, can be used the ferromagnetic layer that one layer of bar paten is grown in high-intensity magnetic field, and bar shaped direction is hung down
Then straight magnetic direction deposits quanta point material, to form compound hair again in the gap of the ferromagnetic layer of bar paten
Photosphere.In the preferred composite luminescence layer being prepared, each quanta point material strip element carriers is by magnetic field
In Lorentz force and internal electric field force collective effect, thus make thus the movement of carrier deflect to form spiral shape
Track can preferably improve Carrier recombination rate, improve the luminous efficiency of device more significantly, and effect is best.It is further excellent
Selection of land, the N=7 or 8.
Further, in above-mentioned steps S01, the ferrimagnet is deposited on cathode or anode, growth has
The step of ferromagnetic layer of bar paten includes: that the mask plate with bar paten is first covered on the cathode or anode
On, recycle magnetron sputtering to deposit the ferrimagnet (as described in Example 1);Or first the ferrimagnet is deposited on
On the cathode or anode, it is then coated with a layer photoresist, then the mask plate with bar paten is covered on the photoresist
On, it is exposed development treatment, last wet etching removes photoresist (as described in Example 2).
Further, in above-mentioned steps S02, quanta point material is deposited on the ferromagnetism material with bar paten
Method in the gap of the bed of material includes any in spin coating, drop coating and printing.
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.
Comparative example 1
A kind of standard QLED device, specific structure ITO/PEDOT:PSS/TFB/CdSe/ZnO/Al.
The specific preparation flow of the QLED device is as follows:
First by the deionized water ultrasonic cleaning 10 minutes of the glass substrate with tin indium oxide (ITO) electrode, then again
It is cleaned by ultrasonic 10 minutes with isopropanol IPA, then dried up surface with nitrogen, is placed in 2h in 80 DEG C of baking oven and dries.Then by base
Piece UVO10 minutes, and in one layer of high molecular polymer PEDOT:PSS hole injection layer of its ito glass surface spin coating.PEDOT:
PSS first uses the polytetrafluoroethylene (PTFE) PTEF filter of 0.2um to filter, and spin coating revolving speed is 3000r.p.m., time 30s, and in air
In 150 DEG C of baking 15min, formed hole injection layer HIL.
Then one layer of hole transmission layer of spin coating on HIL, TFB equally use the PTEF filter of 0.2um to filter, and spin coating revolving speed is
3000r.p.m., time 30s, and 150 DEG C of baking 60min in nitrogen form hole transmission layer HTL.
Following spin coating quantum dot light emitting layer, the same PTEF filter with 0.2um filter, and spin coating revolving speed is
3000r.p.m., time 30s, and 120 DEG C of baking 30min in nitrogen form luminescent layer EML.Following spin coating electronics passes
Defeated layer ZnO, the same PTEF filter with 0.2um filter, and spin coating revolving speed is 1500r.p.m., time 30s, and in nitrogen
120 DEG C of baking 30min form ETL.The electrode A l of one layer of 100nm is finally deposited and is packaged.
Embodiment 1
A kind of novel QLED device, specific device architecture are ITO/PEDOT:PSS/TFB/CdSe&Magnetic Layer/
ZnO/Al;Wherein, Magnetic Layer is FeCoV.
In the specific preparation flow of the novel QLED device, in addition to luminescent layer is different from the normal component of above-mentioned comparative example 1,
Remaining step is completely the same.The luminescent layer preparation flow of the novel QLED device is as follows:
On the substrate for preparing HTL, the mask plate Mask with bar paten is covered on substrate, is splashed using magnetic control
It penetrates and the ferromagnetic layer that ferrimagnet deposition growing goes out bar paten is carried out to it, ferrimagnet is FeCoV herein,
Structure is as shown in Fig. 2.Then drop coating CdSe quantum dot solution forms luminescent layer in the gap of ferromagnetic layer, hereafter locates
It manages step and condition is consistent in above-mentioned comparative example 1.The novel quantum dot hair based on Lorentz force is obtained by this method
Optical device.
The novel QLED device of the standard QLED device of comparative example 1 and the present embodiment is subjected to electrical and optical test hair
Existing, under the driving voltage of 4V, the brightness of the standard QLED device of comparative example 1 is 3000nit, and the novel QLED of the present embodiment
The brightness of device is 5000nit, improves 166% in contrast.At the same time, electroluminescent morphology observation is carried out to device
When, the novel QLED device of the present embodiment is obviously more evenly than the standard QLED device of comparative example 1.
Embodiment 2
A kind of novel QLED device, specific device architecture are ITO/PEDOT:PSS/TFB/CdSe&Magnetic Layer/
ZnO/Al;Wherein, Magnetic Layer is RuFeB.
In the specific preparation flow of the novel QLED device, in addition to luminescent layer is different from the normal component of above-mentioned comparative example 1,
Remaining step is completely the same.The luminescent layer preparation flow of the novel QLED device is as follows:
On the substrate for preparing HIL, the neodymium-iron-boron magnetic material of one layer of 40nm is grown in high-intensity magnetic field, coats one layer
Photoresist, and using having the mask plate of bar paten to be exposed, then develop, using wet etching to magnetic material
Layer performs etching, and finally removes photoresist to form magnetic material bar shaped pattern, bar shaped direction is perpendicular to magnetic direction.Then in magnetic material
Drop coating CdSe quantum dot solution forms one in luminescent layer, this post-processing step and condition and above-mentioned comparative example 1 in the gap of layer
It causes.The novel quantum dot light emitting device based on Lorentz force is obtained by this method.
The novel QLED device of the standard QLED device of comparative example 1 and the present embodiment is subjected to electrical and optical test hair
Existing, under the driving voltage of 4V, the brightness of the standard QLED device of comparative example 1 is 3000nit, and the novel QLED of the present embodiment
The brightness of device is 6000nit, improves 200% in contrast.At the same time, electroluminescent morphology observation is carried out to device
When, the novel QLED device of the present embodiment is obviously more evenly than the standard QLED device of comparative example 1.
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 (12)
1. a kind of light emitting diode with quantum dots, including cathode and anode, and be arranged between the cathode and the anode
Composite luminescence layer, which is characterized in that the composite luminescence layer includes being laid in the surface level of the cathode or the anode
For controlling at least one quanta point material strip element and at least two ferrimagnet bar shaped lists of Carrier composite
Member, and at least one described quanta point material strip element is located between two ferrimagnet bar shaped units.
2. light emitting diode with quantum dots as described in claim 1, which is characterized in that the composite luminescence layer includes N number of described
Quanta point material strip element and the N+1 ferrimagnet bar shaped units, and the quanta point material strip element and institute
State the setting of ferrimagnet bar shaped units alternately;Wherein, N is the integer more than or equal to 1.
3. light emitting diode with quantum dots as claimed in claim 2, which is characterized in that the N=7 or 8.
4. light emitting diode with quantum dots as described in claim 1, which is characterized in that the width of the ferrimagnet bar shaped unit
The width ratio of degree and the quanta point material strip element is greater than 1:1, and the width of the ferrimagnet bar shaped unit is not small
The remanent magnetism of ferrimagnet in 30nm, the ferrimagnet bar shaped unit is greater than 0.5T;Wherein, the ferrimagnet
For permanent magnet material or non-permanent magnet material.
5. light emitting diode with quantum dots as claimed in claim 4, which is characterized in that the non-permanent magnet material is selected from ferrous metal
At least one in simple substance, cobalt metal simple-substance, nickel metal simple-substance, ferrocobalt, iron-nickel alloy, cobalt-nickel alloy and iron cobalt nickel alloy
Kind;And/or
The permanent magnet material is selected from aluminium nickel system permanent-magnet alloy, iron cobalt chromium system permanent-magnet alloy, permanent-magnet ferrite, rare-earth cobalt permanent magnet material
At least one of material and Nd-Fe-B permanent magnet material.
6. light emitting diode with quantum dots as described in claim 1, which is characterized in that the ferrimagnet bar shaped unit is by forever
Magnet material composition.
7. light emitting diode with quantum dots as claimed in claim 6, which is characterized in that the permanent magnet material is selected from aluminium nickel system forever
At least one in magnetic alloy, iron cobalt chromium system permanent-magnet alloy, permanent-magnet ferrite, rare earth cobalt permanent magnets and Nd-Fe-B permanent magnet material
Kind;And/or
The remanent magnetism of the permanent magnet material is greater than 1.1T.
8. such as the described in any item light emitting diode with quantum dots of claim 1-7, which is characterized in that the composite luminescence layer and institute
It states and has been stacked sky acupoints layer between anode;And/or
Electronic work ergosphere has been stacked between the composite luminescence layer and the cathode;And/or
The composite luminescence layer with a thickness of 20nm-60nm.
9. a kind of preparation method of light emitting diode with quantum dots, which comprises the steps of:
Ferrimagnet is provided, the ferrimagnet is deposited on cathode or anode, growing has the ferromagnetic of bar paten
Property material layer;
Quanta point material is deposited in the gap of the ferromagnetic layer with bar paten, obtains composite luminescence layer;
Wherein, the composite luminescence layer includes at least one quanta point material being laid in the surface level of the cathode or the anode
Strip element and at least two ferrimagnet bar shaped units, and at least one described quanta point material strip element is located at two
Between a ferrimagnet bar shaped unit.
10. preparation method as claimed in claim 9, which is characterized in that the composite luminescence layer includes N number of quantum dot material
Expect strip element and the N+1 ferrimagnet bar shaped units, and the quanta point material strip element and the ferromagnetism
The setting of material bar shaped units alternately;Wherein, N is the integer more than or equal to 1.
11. preparation method as claimed in claim 9, which is characterized in that the ferrimagnet is deposited on cathode or anode
On, growing the step of having the ferromagnetic layer of bar paten includes: that the mask plate with bar paten is first covered on institute
It states on cathode or anode, magnetron sputtering is recycled to deposit the ferrimagnet;Or
First the ferrimagnet is deposited on the cathode or anode, is then coated with a layer photoresist, then bar shaped will be had
The mask plate of pattern is covered on the photoresist, is exposed development treatment, and last wet etching removes photoresist.
12. preparation method as claimed in claim 9, which is characterized in that be deposited on quanta point material described with bar chart
Method in the gap of the ferromagnetic layer of case includes any in spin coating, drop coating and printing.
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