CN105826483A - Quantum dot light-emitting diode and preparation method thereof - Google Patents
Quantum dot light-emitting diode and preparation method thereof Download PDFInfo
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- CN105826483A CN105826483A CN201610287986.4A CN201610287986A CN105826483A CN 105826483 A CN105826483 A CN 105826483A CN 201610287986 A CN201610287986 A CN 201610287986A CN 105826483 A CN105826483 A CN 105826483A
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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
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active 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
Abstract
The invention discloses a quantum dot light-emitting diode and preparation method thereof. The preparation method includes the steps of: A. spin-coating a layer of non-acidic lipophilic organic matter on an ITO substrate, and then performing heating and annealing; B. spin-coating PEDOT on the surface of the non-acidic lipophilic organic matter: using PSS as a hole injection layer, and then performing heating and annealing; C. spin-coating a layer of hole transport material on the hole injection layer as a hole transport layer, and then performing thermal treatment; D. depositing a quantum dot light-emitting layer on the surface of the hole transport layer, and then performing thermal treatment; E. depositing an electron transport layer and an electron injection layer on the surface of a quantum dot in sequence; and F. evaporating a cathode on the ITO substrate on which functional layers are deposited. Through the preparation method, processes of ultraviolet oxidation treatment and oxygen plasma treatment are omitted in a manufacturing process, and process steps are simplified. The non-acidic lipophilic organic matter can better sink into holes, and thus a hole injection capability is enhanced, thereby improving the luminous efficiency of a QLED.
Description
Technical field
The present invention relates to Display Technique field, particularly relate to a kind of light emitting diode with quantum dots and preparation method thereof.
Background technology
The photoelectronic property that semiconductor-quantum-point is humorous because having size adjustable, therefore it is widely used in light emitting diode, solaode and biological fluorescent labelling.Quantum dot synthetic technology was through the development of more than 20 years, and people can synthesize various high-quality semiconductor-quantum-point material, and its photoluminescence efficiency can reach more than 85%.Light emitting diode with quantum dots (QLED), because possessing the plurality of advantages such as high brightness, low-power consumption, wide colour gamut, easy processing, obtains and pays close attention in illumination and display field widely and study in recent years.Through development for many years, QLED technology obtains huge development.But, its luminous efficiency of current QLED is the highest, especially blue QLED, is all far below red QLED in its electro-optical efficiency and service life, so limiting QLED application in terms of full-color display；And existing QLED processing technology is more complicated, and cost of manufacture is higher, is unfavorable for the popularization and application of QLED.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of light emitting diode with quantum dots and preparation method thereof, it is intended to solve the problem that existing QLED luminous efficiency is relatively low and relatively costly.
Technical scheme is as follows:
A kind of preparation method of light emitting diode with quantum dots, wherein, including step:
A, the on an ito substrate nonacid lipophile Organic substance of spin coating one layer, then carry out heating anneal；
B, at described nonacid lipophile Organic substance surface spin coating PEDOT:PSS as hole injection layer, then carry out heating anneal；
C, on hole injection layer, one layer of hole mobile material of spin coating, as hole transmission layer, then carries out heat treatment；
D, quantum dot light emitting is deposited upon hole transmission layer surface, then carries out heat treatment；
E, it is sequentially depositing electron transfer layer and electron injecting layer at quantum dot surface；
F, on the ito substrate having deposited each functional layer evaporation cathode.
The preparation method of described light emitting diode with quantum dots, wherein, described nonacid lipophile Organic substance is the derivant of PEDOT:PEG or PEDOT:PEG.
The preparation method of described light emitting diode with quantum dots, wherein, also includes before described step A:
The ito substrate that will be patterned into is sequentially placed in acetone, washing liquid, deionized water and isopropanol and carries out ultrasonic cleaning, after ultrasonic completing, by ito substrate dry for standby.
The preparation method of described light emitting diode with quantum dots, wherein, in described step A, the nonacid lipophile Organic substance thickness of spin coating is 30-50nm.
The preparation method of described light emitting diode with quantum dots, wherein, in described step B, described hole injection layer thickness is 0-100nm.
The preparation method of described light emitting diode with quantum dots, wherein, in described step C, described hole transmission layer is PVK, Poly-TPD or the two mixture, and described thickness of hole transport layer is more than or equal to 10nm.
The preparation method of described light emitting diode with quantum dots, wherein, in described step D, the thickness of described quantum dot light emitting layer is 10-100nm.
The preparation method of described light emitting diode with quantum dots, wherein, in described step E, described electron injecting layer is Ca, Ba, CsF, LiF, CsCO3Or Electrolyte type material, described electron transfer layer is N-shaped zinc oxide, and thickness is 30-60nm.
The preparation method of described light emitting diode with quantum dots, wherein, in described step F, described negative electrode is argent or aluminum.
A kind of light emitting diode with quantum dots, wherein, uses preparation method as above to make.
Beneficial effect: the present invention is by increasing by one layer of nonacid lipophile Organic substance between ito substrate and PEDOT:PSS, it is to avoid the PEDOT:PSS corrosion to ito substrate.Meanwhile, utilize described nonacid lipophile Organic substance so that PEDOT:PSS can be good at its surface filming, eliminate the operations such as Ultraviolet Oxidation process and oxygen plasma process, simplify processing step.It addition, described nonacid lipophile organic HUMO energy level is slightly below ito substrate, therefore can preferably be absorbed in hole, strengthen Hole injection capacity, thus improve QLED luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method preferred embodiment of a kind of light emitting diode with quantum dots of the present invention.
Fig. 2 is the molecular structural formula of PEDOT:PSS in the present invention.
Fig. 3 is the molecular structural formula of the PEDOT:PEG of perchlorate doping in the present invention.
Fig. 4 is the QLED device energy diagram that the present invention prepares.
Fig. 5 is the QLED device junction composition that the present invention prepares.
Detailed description of the invention
The present invention provides a kind of light emitting diode with quantum dots and preparation method thereof, and for making the purpose of the present invention, technical scheme and effect clearer, clear and definite, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Refer to the flow chart of the preparation method preferred embodiment that Fig. 1, Fig. 1 are a kind of light emitting diode with quantum dots of the present invention, as it can be seen, it includes step:
S1, the on an ito substrate nonacid lipophile Organic substance of spin coating one layer, then carry out heating anneal；
S2, at described nonacid lipophile Organic substance surface spin coating PEDOT:PSS as hole injection layer, then carry out heating anneal；
S3, on hole injection layer, one layer of hole mobile material of spin coating, as hole transmission layer, then carries out heat treatment；
S4, quantum dot light emitting is deposited upon hole transmission layer surface, then carries out heat treatment；
S5, it is sequentially depositing electron transfer layer and electron injecting layer at quantum dot surface；
S6, on the ito substrate having deposited each functional layer evaporation cathode.
In QLED prepared by the present invention, use PEDOT:PSS(molecular structural formula as shown in Figure 2) as hole injection layer material, wherein, Polyglycolic acid fibre (PEDOT) not only printing opacity, good stability, and there is high conductivity, but the PEDOT of eigenstate is water insoluble and does not melts, it is difficult to processing film forming.So that PEDOT is solvable, so to its doping p styrene sulfonic acid root anion (PSS) so that PEDOT Yu PSS forms suspension and suspends in aqueous, is then spin coated onto film forming.But PEDOT:PSS itself has acidity, ito substrate surface can there be is certain corrosiveness, cause the electric conductivity affecting anode.
So the present invention uses increases by one layer of nonacid lipophile Organic substance between ito substrate and PEDOT:PSS, thus avoid the PEDOT:PSS directly etching to ito substrate, it is ensured that anode conductivity is unaffected.Simultaneously, described nonacid lipophile Organic substance can well be spin-coated on ito substrate surface and form uniform thin film, further, since the organic surface of nonacid lipophile can form hydrophilic film, PEDOT:PSS is made to can be good at, at its surface filming, improving the film property of PEDOT:PSS.And another important described nonacid lipophile organic HUMO energy level that has the beneficial effect that is slightly below ito substrate, therefore can preferably be absorbed in hole, strengthen Hole injection capacity, thus improve whole QLED luminous efficiency.
Specifically, before described step S1, cleaning step is also included:
The ito substrate that will be patterned into is sequentially placed in acetone, washing liquid, deionized water and isopropanol and carries out ultrasonic cleaning, and the ultrasonic cleaning of above-mentioned each step continues about 15 minutes, after ultrasonic, dries in ito substrate is placed in cleaning oven, standby.
In described step S1, described nonacid lipophile Organic substance uses the derivant of PEDOT:PEG or PEDOT:PEG, PEG or derivatives thereof is i.e. used to substitute the PSS in PEDOT:PSS, oil loving group is i.e. utilized to substitute water soluble group PSS, it is spin-coated on ito substrate surface, owing to the derivant of PEDOT:PEG or PEDOT:PEG can form good hydrophilic film, so the film forming of beneficially PEDOT:PSS, can save and ito substrate is carried out Ultraviolet Oxidation process (UV-Ozonetreatment) and the treatment process of oxygen gas plasma process (Plasmatreatment), so can Simplified flowsheet step, reduce the cost of manufacture of QLED.Preferably, PEG or derivatives thereof is mixed perchlorate, the PEDOT:PEG(PC after doping, i.e. perchlorate doping) its molecular structural formula as it is shown on figure 3, its HOMO energy level of PEDOT:PEG after Can Za is low, as shown in Figure 4, can more effectively inject hole.It addition, the derivant of PEG can be with other alcohols materials, such as n-butyl alcohol or isobutanol etc..
The described organic thickness of nonacid lipophile is preferably 30-50nm, carries out heating anneal process after spin coating completes, and ito substrate is specifically placed on the warm table of 150 DEG C heating 15 minutes, to remove unnecessary solvent.
The present invention is by adding one layer of derivant doped with PEDOT:PEG or PEDOT:PEG of perchlorate between traditional hole injection layer PEDOT:PSS and ito substrate, one solves the PEDOT:PSS corrosion problems to ito substrate, it two improves PEDOT:PSS film forming homogeneity question on an ito substrate, reduces cost；It three improves QLED luminous efficiency.
In described step S2, the upper spin coating PEDOT:PSS of nonacid lipophile Organic substance (such as PEDOT:PEG or derivatives thereof) after annealing is as hole injection layer, the thickness of this layer is preferably 0-100nm, then carry out heating anneal process, specifically the ito substrate having made hole injection layer is placed on the warm table of 150 DEG C heating 15 minutes.
In described step S3, on PEDOT:PSS, one layer of hole mobile material of spin coating is as hole transmission layer, this hole mobile material can be PVK(Polyvinyl carbazole) or Poly-TPD, it can also be their mixture, can certainly be other high performance hole mobile material, the thickness of hole transport layer deposited be preferably greater than or equal to 10nm.After having deposited hole transmission layer, need to be placed on heat treatment on warm table, the condition of heat treatment be temperature be 150 DEG C, 15-30 minute heat time heating time, such as 20 minutes, with remove residual solvent.
In described step S4, after the ito substrate of step S3 heat treatment cools down, quantum dot light emitting being deposited upon hole transmission layer surface, the thickness of quantum dot light emitting layer is preferably between 10-100nm.After having deposited quantum dot light emitting layer, place it in heat treated 10 minutes on the warm table of 80 DEG C, to remove the solvent of residual.
In described step S5, it is sequentially depositing electron transfer layer and electron injecting layer on quantum dot light emitting layer surface, wherein electron transfer layer preferably has the N-shaped zinc oxide of high electronic transmission performance, its preferably thickness is 30-60nm, electron injecting layer material can select the metals such as Ca or Ba of low work function, CsF, LiF or CsCO can also be selected3Deng compound, certainly can also is that other Electrolyte type material.
In described step S6, the ito substrate having deposited each functional layer is placed in evaporation storehouse, by mask plate heat evaporation layer of metal is silver-colored or aluminum is as negative electrode, the most described negative electrode is preferably argent or aluminum, the thickness of negative electrode is preferably 100nm, so far, prepared by device, as shown in Figure 5, prepare its concrete structure of QLED of one the most successively: ito substrate 11, PEDOT:PEG12, hole injection layer 13(PEDOT:PSS), hole transmission layer 14(PVK), quantum dot light emitting layer 15(QD), electron transfer layer/electron injecting layer 16(ETL/EIL), 17 negative electrodes (Al).
The present invention also provides for a kind of light emitting diode with quantum dots, and it uses preparation method as above to make.
In sum, the present invention is by increasing by one layer of nonacid lipophile Organic substance between ito substrate and PEDOT:PSS, it is to avoid the PEDOT:PSS corrosion to ito substrate.Meanwhile, utilize described nonacid lipophile Organic substance so that PEDOT:PSS can be good at its surface filming, eliminate the operations such as Ultraviolet Oxidation process and oxygen plasma process, simplify processing step.It addition, described nonacid lipophile organic HUMO energy level is slightly below ito substrate, therefore can preferably be absorbed in hole, strengthen Hole injection capacity, thus improve QLED luminous efficiency.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, all these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (10)
1. the preparation method of a light emitting diode with quantum dots, it is characterised in that include step:
A, the on an ito substrate nonacid lipophile Organic substance of spin coating one layer, then carry out heating anneal；
B, at described nonacid lipophile Organic substance surface spin coating PEDOT:PSS as hole injection layer, then carry out heating anneal；
C, on hole injection layer, one layer of hole mobile material of spin coating, as hole transmission layer, then carries out heat treatment；
D, quantum dot light emitting is deposited upon hole transmission layer surface, then carries out heat treatment；
E, it is sequentially depositing electron transfer layer and electron injecting layer at quantum dot surface；
F, on the ito substrate having deposited each functional layer evaporation cathode.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that described nonacid lipophile Organic substance is the derivant of PEDOT:PEG or PEDOT:PEG.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that also include before described step A:
The ito substrate that will be patterned into is sequentially placed in acetone, washing liquid, deionized water and isopropanol and carries out ultrasonic cleaning, after ultrasonic completing, by ito substrate dry for standby.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that in described step A, the nonacid lipophile Organic substance thickness of spin coating is 30-50nm.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that in described step B, described hole injection layer thickness is 0-100nm.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that in described step C, described hole transmission layer is PVK, Poly-TPD or the two mixture, and described thickness of hole transport layer is more than or equal to 10nm.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that in described step D, the thickness of described quantum dot light emitting layer is 10-100nm.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that in described step E, described electron injecting layer is Ca, Ba, CsF, LiF, CsCO3Or Electrolyte type material, described electron transfer layer is N-shaped zinc oxide, and thickness is 30-60nm.
The preparation method of light emitting diode with quantum dots the most according to claim 1, it is characterised in that in described step F, described negative electrode is argent or aluminum.
10. a light emitting diode with quantum dots, it is characterised in that use the preparation method as described in any one of claim 1 ~ 9 to make.
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| CN106374046A (en) * | 2016-09-12 | 2017-02-01 | Tcl集团股份有限公司 | Positively-arranged structure quantum dot light-emitting diode and fabrication method thereof |
| CN106784212A (en) * | 2016-12-15 | 2017-05-31 | Tcl集团股份有限公司 | Qled and preparation method thereof |
| CN106935719A (en) * | 2017-02-24 | 2017-07-07 | 深圳市华星光电技术有限公司 | A kind of quanta point electroluminescent device and preparation method thereof |
| CN108023024A (en) * | 2016-11-01 | 2018-05-11 | 乐金显示有限公司 | Light emitting diode with quantum dots and the quantum dot display device for including it |
| CN110098339A (en) * | 2018-01-31 | 2019-08-06 | 昆山工研院新型平板显示技术中心有限公司 | A kind of light emitting diode with quantum dots QLED device and preparation method thereof, device |
| CN110400826A (en) * | 2019-07-09 | 2019-11-01 | 深圳市华星光电技术有限公司 | Display panel and display device |
| WO2020108070A1 (en) * | 2018-11-26 | 2020-06-04 | Tcl科技集团股份有限公司 | Preparing method for quantum dot light-emitting diode |
| CN114122275A (en) * | 2021-11-26 | 2022-03-01 | 电子科技大学中山学院 | Transition metal chloride near-ultraviolet light-emitting device and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106374046A (en) * | 2016-09-12 | 2017-02-01 | Tcl集团股份有限公司 | Positively-arranged structure quantum dot light-emitting diode and fabrication method thereof |
| CN108023024A (en) * | 2016-11-01 | 2018-05-11 | 乐金显示有限公司 | Light emitting diode with quantum dots and the quantum dot display device for including it |
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| CN106784212A (en) * | 2016-12-15 | 2017-05-31 | Tcl集团股份有限公司 | Qled and preparation method thereof |
| CN106784212B (en) * | 2016-12-15 | 2019-09-17 | Tcl集团股份有限公司 | QLED and preparation method thereof |
| CN106935719A (en) * | 2017-02-24 | 2017-07-07 | 深圳市华星光电技术有限公司 | A kind of quanta point electroluminescent device and preparation method thereof |
| US10615357B2 (en) | 2017-02-24 | 2020-04-07 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Quantum dots light-emitting diode and method for manufacturing the same |
| CN110098339A (en) * | 2018-01-31 | 2019-08-06 | 昆山工研院新型平板显示技术中心有限公司 | A kind of light emitting diode with quantum dots QLED device and preparation method thereof, device |
| CN110098339B (en) * | 2018-01-31 | 2020-04-17 | 昆山工研院新型平板显示技术中心有限公司 | Quantum dot light-emitting diode (QLED) device and manufacturing method and device thereof |
| WO2020108070A1 (en) * | 2018-11-26 | 2020-06-04 | Tcl科技集团股份有限公司 | Preparing method for quantum dot light-emitting diode |
| CN110400826A (en) * | 2019-07-09 | 2019-11-01 | 深圳市华星光电技术有限公司 | Display panel and display device |
| CN114122275A (en) * | 2021-11-26 | 2022-03-01 | 电子科技大学中山学院 | Transition metal chloride near-ultraviolet light-emitting device and preparation method thereof |
| CN114122275B (en) * | 2021-11-26 | 2023-06-09 | 电子科技大学中山学院 | Transition metal chloride near ultraviolet light-emitting device and preparation method thereof |
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