CN110416420A - 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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- CN110416420A CN110416420A CN201810403828.XA CN201810403828A CN110416420A CN 110416420 A CN110416420 A CN 110416420A CN 201810403828 A CN201810403828 A CN 201810403828A CN 110416420 A CN110416420 A CN 110416420A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
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Abstract
The present invention provides a kind of light emitting diode with quantum dots, including the anode and cathode being oppositely arranged, and it is provided with quantum dot light emitting layer between the anode and the cathode, the first functional layer is provided between the cathode and the quantum dot light emitting layer, and first functional layer is electron transfer layer, and the material of the electron transfer layer is silicon doping zinc-oxide.
Description
Technical field
The invention belongs to technical field of flat panel display more particularly to a kind of light emitting diode with quantum dots and preparation method thereof.
Background technique
Semiconductor-quantum-point has the humorous optico-electronic properties of size adjustable, be widely used in light emitting diode,
Solar battery and biological fluorescent labelling.Quantum dot synthetic technology passes through development in more than 20 years, and people can synthesize respectively
The nano material of kind high quality, photoluminescence efficiency can achieve 85% or more.Since quantum dot has dimension adjustable
The features such as luminous, line width that shines, photoluminescence efficiency height and thermal stability, therefore using quantum dot as the quantum dot of luminescent layer
Light emitting diode (QD-LED) is next-generation display and the solid-state lighting light source of great potential.Light emitting diode with quantum dots (QLED)
It is obtained widely in illumination and display field in recent years because having many advantages, such as high brightness, low-power consumption, wide colour gamut, easy processing
Concern and research.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 external quantum efficiency highest at present alreadys exceed or close to 20%, shows the interior quantum of red green QLED
The limit of the efficiency actually already close to 100%.However, at present not as the indispensable blue QLED of the full-color display of high-performance
By being in electro-optical efficiency or on service life all far below red green QLED, to limit QLED in full-color display side
The application in face.
For traditional QLED device, device efficiency has had reached the needs of display technology, but its stability is
Restrict an important technology defect of its application.Therefore, the raising QLED device stability of appropriateness is and its important.Its
In, an important reason for restricting QLED stability is exactly short circuit current, and short circuit current can make device thermal power increase, shadow
Ring device stability and efficiency.Wherein, the principal element for causing shorted devices electric current big include impurity particle therein, film not
Smooth and ITO electrode irregularities etc..
Summary of the invention
The purpose of the present invention is to provide a kind of light emitting diode with quantum dots and preparation method thereof, it is intended to solve existing amount
The bad problem of sub- point luminescent diode stability.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of light emitting diode with quantum dots, including the anode and cathode being oppositely arranged, and in the anode and the cathode
Between be provided with quantum dot light emitting layer, the first functional layer is provided between the cathode and the quantum dot light emitting layer, and described
First functional layer is electron transfer layer, and the material of the electron transfer layer is silicon doping zinc-oxide.
And a kind of preparation method of light emitting diode with quantum dots, comprising the following steps:
Cathode is provided；
The first functional layer is prepared on the cathode, and first functional layer is the electron-transport of silicon doped zinc oxide material
Layer；
In the electron-transport layer surface preparation amount point luminescent layer；
Anode is prepared on the quantum dot light emitting layer.
Light emitting diode with quantum dots provided by the invention is arranged silicon between cathode and the quantum dot light emitting layer and adulterates oxygen
Change the electron transfer layer of Zinc material, i.e. it is steady to improve device under the premise of increasing device efficiency, excitation purity for the first functional layer
It is qualitative.
Firstly, introducing first functional layer, for the purer ZnO of silicon doped zinc oxide material, there is lower electricity
Transport factor, but for the light emitting diode with quantum dots that hole transport layer material is organic material, due to general organic
Material cavity transmission ability is significantly less than inorganic material electron transport ability, and the silicon with lower electron transport ability adulterates oxidation
Zinc material can better equilbrium carrier, reduce nonradiative transition, reduce device temperature, improve device stability.
Secondly, the work function of silicon doped zinc oxide material is also small compared with pure ZnO material, therefore, first functional layer can be with
Ohmic contact is formed with ITO cathode, reduces open-circuit voltage.In addition, passing through the electron transfer layer for increasing silicon doped zinc oxide material
Thickness, to the greatest extent can reduction cathode surface out-of-flatness caused by short circuit current, further increase device stability.
The preparation method of light emitting diode with quantum dots provided by the invention need to only prepare silicon doping zinc-oxide material on cathode
The electron transfer layer of material, is then sequentially prepared light emitting diode with quantum dots and anode.This method technique relative maturity, simply
Controllably, it is advantageously implemented large-scale production.
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.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of light emitting diode with quantum dots, including the anode and cathode being oppositely arranged, and
It is provided with quantum dot light emitting layer between the anode and the cathode, is provided between the cathode and the quantum dot light emitting layer
First functional layer, and first functional layer is electron transfer layer, and the material of the electron transfer layer is silicon doping zinc-oxide.
Silicon is arranged between cathode and the quantum dot light emitting layer in light emitting diode with quantum dots provided in an embodiment of the present invention
The electron transfer layer of doped zinc oxide material, i.e. the first functional layer can improve under the premise of increasing device efficiency, excitation purity
Device stability.
Firstly, introducing first functional layer, for the purer ZnO of silicon doped zinc oxide material, there is lower electricity
Transport factor, but for the light emitting diode with quantum dots that hole transport layer material is organic material, due to general organic
Material cavity transmission ability is significantly less than inorganic material electron transport ability, and the silicon with lower electron transport ability adulterates oxidation
Zinc material can better equilbrium carrier, reduce nonradiative transition, reduce device temperature, improve device stability.
Secondly, the work function of silicon doped zinc oxide material is also small compared with pure ZnO material, therefore, first functional layer can be with
Ohmic contact is formed with ITO cathode, reduces open-circuit voltage.In addition, passing through the electron transfer layer for increasing silicon doped zinc oxide material
Thickness, to the greatest extent can reduction cathode surface out-of-flatness caused by short circuit current, further increase device stability.
In the embodiment of the present invention, the amorphous Zn of material of first functional layermSinThe value of m, n are to charge in O material
Transmission is affected.The value range of m is 0.8-0.95, the work content for the compound that the value range of n is formed when being 0.05-0.2
Several and ITO is close, forms Ohmic contact, and having can be with hole injection layer with the electron mobility of the order of magnitude.When zinc salt mistake
Amount, when silicon is a small amount of, Zn content is more in system, ZnmSinThe electron mobility of O is larger, but its work function is also larger, be unfavorable for
ITO forms Ohmic contact, reduces injection barrier.Conversely, ZnmSinThe resistivity of O is too big, is unfavorable for electron-transport.
Preferably, the silicon doping zinc-oxide is ZnmSinO, wherein the value range of m is 0.8-0.95, the value model of n
It encloses for 0.05-0.2.Preferred above-mentioned silicon doping zinc-oxide, can preferably improve device stability.
It is further preferred that the electron transfer layer with a thickness of 130-280nm.The embodiment of the present invention is by being added thickness
For the amorphous Zn of 130-280nmmSinThe electron transfer layer of O material can form optics inside light emitting diode with quantum dots
Microcavity can increase the luminous intensity of resonance wavelength using optical microcavity structure, the luminescent spectrum that narrows improves excitation purity, improves device
The luminous efficiency of part.
In the embodiment of the present invention, according to d=n λ (d is optical path difference, and λ is emission wavelength), the thickness of first functional layer
According to the difference of the luminescent color of light emitting diode with quantum dots, can advanced optimize.As a kind of implementation situation, the quantum
Point luminescent diode is green quantum point luminescent diode, the and (ZnmSinO material) electron transfer layer with a thickness of 170-
250nm can more effectively reinforce resonating at this time, increase light extraction efficiency.As；Another implementation situation, the quantum dot hair
Optical diode is blue light quantum point light emitting diode, the and (ZnmSinO material) electron transfer layer with a thickness of 130-
220nm can more effectively reinforce resonating at this time, increase light extraction efficiency.As another implementation situation, the quantum dot light emitting
Diode is red quantum point luminescent diode, the and (ZnmSinO material) electron transfer layer with a thickness of 210-280nm,
It can more effectively reinforce resonating at this time, increase light extraction efficiency.
In the embodiment of the present invention, in order to advantageously promote hole transport, it is preferred that sent out in the anode and the quantum dot
The second functional layer is provided between photosphere, and second functional layer is hole transmission layer.The hole transmission layer can be selected from
Poly- (9,9- dioctyl fluorene-CO-N- (4- butyl phenyl) diphenylamines), polyvinylcarbazole, it is poly- (bis- (4- the butyl phenyl)-N of N, N',
Bis- (phenyl) benzidine of N'-), poly- (double-N of 9,9- dioctyl fluorene -co-, N- phenyl -1,4- phenylenediamine), 4,4 ', 4 "-three (clicks
Azoles -9- base) triphenylamine, 4,4'- bis- (9- carbazole) biphenyl, but not limited to this.
Second functional layer with a thickness of 0-100nm.It is further preferred that second functional layer with a thickness of 40-
50nm.If it is described it is too thin if electric conductivity it is weaker, and cause both hole and electron uneven, luminous zone may electron transfer layer without
Quantum dot layer；It is too thick, it is unfavorable for injecting.
In the embodiment of the present invention, the anode can choose but be not limited to metal anode, and the cathode can choose but not
It is limited to ITO cathode.
Quantum dot in the quantum dot layer can for II-VI group compound, III-V compound, II-V compounds of group,
The monocrystalline that III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group or IV race are formed
At least one of semiconducting compound, be also possible to II-VI group compound, III-V compound, II-V compounds of group,
The binary that III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group or IV race are formed
Or at least one of semiconducting compound of polynary core-shell structure, it can also be monocrystalline semiconductor compounds and core-shell structure
The mixture that semiconducting compound is formed.In the embodiment of the present invention, the quantum dot light emitting layer with a thickness of 10-100nm.
Light emitting diode with quantum dots provided in an embodiment of the present invention can be prepared by following methods.
And the embodiment of the invention also provides a kind of preparation methods of light emitting diode with quantum dots, which is characterized in that packet
Include following steps:
S01., cathode is provided；
S02. the first functional layer is prepared on the cathode, and first functional layer is the electronics of silicon doped zinc oxide material
Transport layer；
S03. quantum dot light emitting layer is sequentially prepared in the electron-transport layer surface；
S04. anode is prepared on the quantum dot light emitting layer.
The preparation method of light emitting diode with quantum dots provided in an embodiment of the present invention need to only prepare silicon doping oxygen on cathode
The electron transfer layer for changing Zinc material, is then sequentially prepared light emitting diode with quantum dots and anode.This method technique relative at
It is ripe, it is simple controllable, it is advantageously implemented large-scale production.
Specifically, in above-mentioned steps S01, it is preferred that start the cleaning processing cathode.As particular preferred embodiment, clearly
The method for washing processing are as follows: the cathode base that will be patterned into is placed in acetone, washing lotion, deionized water and isopropanol in order and carries out
Ultrasonic cleaning, each of the above step ultrasound are both needed to continue 10-25m minutes, more preferably 15 minutes.Cathode is put after the completion of ultrasound
It is placed in cleaning oven and is dried for standby.
In above-mentioned steps S02, the first functional layer is prepared on the cathode, it is preferred that the silicon doping zinc-oxide is
ZnmSinO, wherein the value range of m is 0.8-0.95, and the value range of n is 0.05-0.2.It is specific preferred, first function
Ergosphere the preparation method comprises the following steps:
Zinc salt, silicate are provided, after the two is mixed to form mixed raw material, using argon gas as protective gas, made with oxygen
For working gas, amorphous Zn is prepared by magnetron sputteringmSinThe electron transfer layer of O material.Zinc salt and silicate is former
Material is being passed through Ar and O by the method for sputtering2It is deposited under conditions of gaseous mixture in ITO cathode substrate.Wherein, O2Mixing is provided
After raw material, using argon gas as protective gas, using oxygen as working gas, silicon doping zinc-oxide is prepared by magnetron sputtering
O element in mixture.By magnetron sputtering, unbodied Zn can be obtainedmSinO material.
Wherein, the zinc salt is selected from least one of zinc sulfate, zinc chloride, zinc nitrate.The zinc salt and the silicic acid
The molar ratio of salt is m:n.
In above-mentioned steps S03, in the electron-transport layer surface preparation amount point luminescent layer, further preferred is being prepared
It further include that the second functional layer is prepared on the quantum dot light emitting layer after quantum dot light emitting layer, second functional layer is sky
Cave transport layer.
In above-mentioned steps S04, anode is prepared on the quantum dot light emitting layer, can be realized using conventional method.
In the embodiment of the present invention, the quantum dot light emitting layer, second functional layer preparation method, including chemical method
And physical method, wherein the physical method includes physical coating method and solution processing method.Specifically, chemical method includes: chemical gaseous phase
Sedimentation, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitation.The physical coating method packet
It includes: thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, physical vaporous deposition, original
Sublayer sedimentation, pulsed laser deposition etc..The solution processing method includes spin-coating method, print process, impact system, Best-Effort request
Method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip rubbing method.The embodiment of the present invention preferably uses molten
Uniform and fine and close interface-modifying layer is prepared in liquid processing method.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of light emitting diode with quantum dots, comprising the following steps:
S11. the ito substrate that will be patterned into is placed in acetone in order, washing lotion, and ultrasound is carried out in deionized water and isopropanol
Cleaning, each of the above step ultrasound are both needed to lasting 15 minutes or so.ITO is placed in cleaning oven after the completion of the ultrasound dry it is standby
With.
S12. after ITO substrate is dry, one layer of Zn is deposited by the method for sputtering on itmSinO electron transfer layer.
S13. after upper sheet is cooled to room temperature, deposit QD on it, this layer with a thickness of 20-40nm, be not required to heat.
Later, deposition of hole transport layer TFB, with a thickness of 40nm.Piece is placed on to 100 DEG C of heating after the completion of the deposition of this step
It is heated 30 minutes on platform, removes remaining solvent.Pass through exposure mask finally, piece for having deposited each functional layer is placed in vapor deposition storehouse
The metallic silver of one layer of 100nm of plate hot evaporation is as anode.Device preparation is completed.
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 (13)
1. a kind of light emitting diode with quantum dots, which is characterized in that including the anode and cathode being oppositely arranged, and in the anode and
It is provided with quantum dot light emitting layer between the cathode, the first function is provided between the cathode and the quantum dot light emitting layer
Layer, and first functional layer is electron transfer layer, and the material of the electron transfer layer is silicon doping zinc-oxide.
2. light emitting diode with quantum dots as described in claim 1, which is characterized in that the silicon doping zinc-oxide is ZnmSinO,
Wherein, the value range of m is 0.8-0.95, and the value range of n is 0.05-0.2.
3. light emitting diode with quantum dots as described in claim 1, which is characterized in that the electron transfer layer with a thickness of 130-
280nm。
4. light emitting diode with quantum dots as claimed in claim 3, which is characterized in that the light emitting diode with quantum dots is green light
Light emitting diode with quantum dots, and the electron transfer layer with a thickness of 170-250nm.
5. light emitting diode with quantum dots as claimed in claim 3, which is characterized in that the light emitting diode with quantum dots is blue light
Light emitting diode with quantum dots, and the electron transfer layer with a thickness of 130-220nm.
6. light emitting diode with quantum dots as claimed in claim 3, which is characterized in that the light emitting diode with quantum dots is feux rouges
Light emitting diode with quantum dots, and the electron transfer layer with a thickness of 210-280nm.
7. light emitting diode with quantum dots as claimed in any one of claims 1 to 6, which is characterized in that in the anode and the amount
It is provided with the second functional layer between son point luminescent layer, and second functional layer is hole transmission layer.
8. light emitting diode with quantum dots as claimed in any one of claims 1 to 6, which is characterized in that the thickness of second functional layer
Degree is 0-100nm.
9. light emitting diode with quantum dots as claimed in claim 8, which is characterized in that second functional layer with a thickness of 40-
50nm。
10. the preparation method that a kind of quantum dot determines light emitting diode, which comprises the following steps:
Cathode is provided；
The first functional layer is prepared on the cathode, and first functional layer is the electron transfer layer of silicon doped zinc oxide material；
In the electron-transport layer surface preparation amount point luminescent layer；
Anode is prepared on the quantum dot light emitting layer.
11. the preparation method of light emitting diode with quantum dots as claimed in claim 10, which is characterized in that the silicon doping oxidation
Zinc is ZnmSinO, wherein the value range of m is 0.8-0.95, and the value range of n is 0.05-0.2.
12. the preparation method of light emitting diode with quantum dots as claimed in claim 11, which is characterized in that first functional layer
The preparation method comprises the following steps:
Zinc salt, silicate are provided, after the two is mixed to form mixed raw material, using argon gas as protective gas, using oxygen as work
Make gas, the electron transfer layer of silicon doped zinc oxide material is prepared by magnetron sputtering.
13. the preparation method of light emitting diode with quantum dots as claimed in claim 12, which is characterized in that the zinc salt is selected from sulphur
At least one of sour zinc, zinc chloride, zinc nitrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120947A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN114079027A (en) * | 2020-12-31 | 2022-02-22 | 广东聚华印刷显示技术有限公司 | Light emitting device and method of manufacturing the same |
-
2018
- 2018-04-28 CN CN201810403828.XA patent/CN110416420B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120947A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN114079027A (en) * | 2020-12-31 | 2022-02-22 | 广东聚华印刷显示技术有限公司 | Light emitting device and method of manufacturing the same |
| CN114079027B (en) * | 2020-12-31 | 2023-10-31 | 广东聚华印刷显示技术有限公司 | Light emitting device and method of manufacturing the same |
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