CN108389982A - Light-emitting diode assembly and display device - Google Patents
Light-emitting diode assembly and display device Download PDFInfo
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- CN108389982A CN108389982A CN201810093671.5A CN201810093671A CN108389982A CN 108389982 A CN108389982 A CN 108389982A CN 201810093671 A CN201810093671 A CN 201810093671A CN 108389982 A CN108389982 A CN 108389982A
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Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- 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 present invention provides a kind of light-emitting diode assemblies, including substrate, anode, hole transmission layer, luminescent layer, electron transfer layer and cathode, it is characterized in that, luminescent layer is combined by quantum dot and energy transfer molecule, energy transfer molecule is crosslinked with quantum dot by click chemistry.Energy transfer molecule has high electrons carrier injectability as the decentralized medium of quantum dot, and the exciton in energy transfer molecule can be promoted to generate, and realizes the effective energy transfer between energy transfer molecule to fluorescence quantum.Under certain voltage, the present apparatus can shine in the wave-length coverage of 380 900nm, emission maximum peak value optical range from ultraviolet to dark red.The invention also discloses a kind of preparation method of light-emitting diode assembly and electronic display units.
Description
Divisional application
The application be August in 2016 submit within 23rd entitled " include the light emitting diode of quantum dot and energy transfer molecule
The divisional application of the Chinese patent application " 201610704608.1 " of device and preparation method thereof, display device ".
Technical field
The application belongs to display field more particularly to a kind of light-emitting diode assembly and display device.
Background technology
Quantum dot is the semiconductor nanocrystal of nano-scale, has controllable surface chemistry conditions and depending on size
Optical property.Quantum dot can be with luminescence generated by light and electroluminescent.In display device applications, quantum dot is not less than organic hair
Optical diode (OLED), and has the following advantages：1) service life, quantum dot are made of inorganic core, have the potential long-life；2)
Colour purity, the color category that quantum dot generates is very more, and improved Super-vision experience is provided for terminal user；3) flexibly
Property, quantum dot is solvable in water and nonaqueous solvents, this provides more choosings to prepare the display device of size of all kinds
It selects, and reduces production, operation and processing cost.
One typical QLED structure deposited one layer of organic cavity transmission layer, then thereon by a transparent anode
Redeposited one layer of Colloidal Quantum Dots single layer, an organic electron transport layer and a metallic cathode.In QLED there are two types of
Electroluminescent mechanism is suggested.The first mechanism is the electrons and holes carrier transmitted by organic charge transport layer, direct
It is injected into quantum dot, they can form the excitation state that can radiate recombination here.Second of mechanism is to be coated on quantum dot
The high energy excitation state formed in organic molecule around diaphragm, by excited energy resonance transfer to quantum dot, then so that amount
Son point shines.
Although being improved in equipment assembly and the synthesis of high quality quantum dot, as the mechanism of QLED：Amount
Again compound middle formation of the son point excitation state in hole and electronics.Hole comes from organic or macromolecule layer, and electronics is also had by oneself
Machine and macromolecule layer.There are two main problems for this mechanism.First, a part of hole and/or electricity that organic and polymer layer is formed
Son directly recombinates and causes the transmitting of principal matrix.Overcoming the problems, such as a kind of this method is, is made by a phase separation
Quantum dot single layer is clipped between organic electronic and hole transmission layer, to establish the hydridization with external quantum efficiency 0.5%
Organic/inorganic multilayer QLED structures.It is assumed that thin quantum dot layer helps to mitigate the influence of low quantum dot carrier mobility, then
Above-mentioned sandwich will be helpful to equilbrium carrier injection.However, under the conditions of highlighted, shown these devices
The performance significantly emitted from organic substrate.The major defect of second of QLED is that it low internal quantum efficiency occurs, this is originated from
The presence of the energy level barrier of quantum dot, especially when they have coated one layer of organic ligand, due to semiconductor nano
Body have low electric conductivity so that carrier is more difficult to be injected into quantum dot, thus the problem of low quantum efficiency be degrading.
Invention content
For the above problem existing for existing QLED display devices, the present invention provides a kind of light-emitting diode assembly, energy
Enough charges that effectively promoted are injected into luminescent layer.
The purpose of the present invention is to provide a kind of light-emitting diode assemblies, including：
A) hole transmission layer, for injection and transporting holes；
B) luminescent layer is contacted with the hole transmission layer；
C) electron transfer layer is contacted with the luminescent layer, for injecting and transmitting electronics to the luminescent layer；
D) anode and cathode is used for DC voltage, electric current is made to flow in a device, and with ultraviolet light, visible light or close
The form of infrared light sends out radiation, and light-emitting diode assembly is made to shine；
The luminescent layer includes quantum dot and energy transfer molecule, point of the energy transfer molecule as the quantum dot
Dispersion media has high electronics and/or holoe carrier injectability, and is crosslinked by click chemistry with the quantum dot.
Energy transfer molecule has both the effect of quantum dot dispersion solvent and energy transfer in the present invention.It is built by this method
QLED, from the energy transfer molecule being blended near quantum dot surface to the energy transfer process of quantum dot core, the amount of promoting
The injection of charge, especially injection of the electronics from cathode to quantum dot in son point.
Preferably, when adding the DC voltage of 0-30V between a cathode and an anode, light-emitting diode assembly has wavelength
Electroluminescent within the scope of 380-900nm.
Preferably, energy transfer molecule has high fluorescence quantum efficiency, oxidation-reduction quality reversible in nonaqueous electrolyte
Matter and the band gap wider than quantum dot, to obtain efficient electronics and/or holoe carrier injection.
Preferably, quantum dot is cross-linked to form composite layer, wherein energy transfer point with energy transfer molecule by click chemistry
The ligand terminal groups that attached bag includes one kind quantum dot of the acetenyl either in azido functional group include acetenyl or azido two
Any one in person；After Overheating Treatment, quantum dot and energy transfer molecule completion are cross-linked to form composite layer.
Preferably, energy transfer molecule be molecule class, oligomeric species either polymerize species including following molecular group or he
At least one of derivative：
Wherein R1, R2, R3For-(CH2) x- (CH=CH) y- (CH2) z-R；R be following group in one kind-H ,-Cl ,-
Br、-I、-OH、-OCH3、-OC2H5、-CHO、-COOCH3、-COOH、-CONH2、-COCl、-COBr、-COI、-NH2、-N+
(CH3)3、-C(CH3)3,-CH=CH2、-CCH、-C6H5、-C5H5、-N3、-OCN、-NCO、-CN、-NC、-NO2、-C5H4N、-SH、-
S-S-H、-SOCH3、-SO2H、-SCN、-NCS、-CSH、-PH2, phosphono, phosphate, guanyl-, cytimidine base, adenine
Base, thymine base.For energy transfer molecule tool with above structure there are two functional group site, P=O functional groups are conducive to electricity
The injection of subvector point, heterocycle nitrogen functional group are conducive to the injection in hole.
Organic metal fluorescent emitter carries out hydridization with three wide tape gap substrates, realizes the QLED of high brightness.It is preferred that
Ground, energy transfer molecule 2,7- bis- (diphenyl phosphine oxide) -9,9- octyls fluorenes (PO8) have long alkyl chain in PO8 molecules
Object is closed, the ligand on incorporating quantum point surface is carried out.The presence of PO8 can effectively promote electron injection to quantum dot/PO8 hydridization
In layer, and stop that hole carriers enter hybrid layer, can so reduce the electric current under same applied voltage.
Preferably, the composite layer of quantum dot and PO8 are prepared by the method for spin coating mixed solution.
Preferably, substrate is glass or flexible substrate.
Preferably, anode material is conductive metal oxide or conducting polymer.
Preferably, cathode material includes any one in Al, Ca, Ba, Ca/Al, Ag.
Preferably, hole transmission layer includes one kind in the molecule with the following group：Tertiary aromatic amine, thiophene oligomers, thiophene polymeric
Object, pyrroles's oligomer, vinyl penylene oligomer, vinyl polyphenylene polymer, vinylcarbazole oligomer, vinyl carbazole are poly-
Close object, fluorine oligomer, fluoropolymer, acetenyl penylene oligomer, acetenyl polyphenylene polymer, penylene oligomer, penylene polymerization
Object, oligomerization of acetylene object, acetylene polymer, phthalocyanine, phthalocyanine derivates, porphyrine and seaweed alkali derivant.
Preferably, electron transfer layer includes at least one of the molecule with the following group：Furodiazole, oxadiazole classes derive
Object, oxazole class, oxazole analog derivative, isoxazole, Isoxazole derivative, thiazole, thiazole, 1,2,3-triazoles, 1,2,3-
Triazole derivative, 1,3,5-triazines class, 1,3,5-triazines class compound derivatives, quinoxaline, quinoxaline derivant, pyrroles are oligomeric
Object, azole polymer, vinyl penylene oligomer, vinyl polyphenylene polymer, vinylcarbazole oligomer, vinyl carbazole are poly-
Close object, fluorine oligomer, fluoropolymer, acetenyl penylene oligomer, acetenyl polyphenylene polymer, penylene oligomer, penylene polymerization
Object, thiophene oligomers, thiophen polymer, oligomerization of acetylene object, acetylene polymer, TiO2Nano particle, ZnO nano particle, SnO receive
Rice grain, gold nano grain and silver nano-grain.
Preferably, the quantum dot includes one kind in the quantum dot with lower structure：
A) ZnSe/ZnSeS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
B) ZnTe/ZnSe/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
C) ZnTe/ZnTeS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
D) CdSe/CdZnS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
E) CdSe/CdZnSe/ZnSe/ZnS core shells/shell/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
F) CdTe/CdZnS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
G) CdS/ZnS core/shell structures, CdS/ZnSe/ZnS core shells/shell structure or CdZnS/ZnSe/ZnS core shells/shell
Structure quantum point, size is within the scope of 1.5-10nm；
H) CdTe/InP/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
I) InP/ZnS core/shell structures quantum dot, size is within the scope of 1.5-9nm；
J) additive Mn ZnSe:Mn2+/ ZnS core/core-shell structure quantum dots, ZnSe/ZnS:Mn2+/ ZnS core/shell/shell structure quantum
Point or ZnS:Mn2+/ ZnS core/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
K) Copper-cladding Aluminum Bar ZnS:Cu+/ ZnS core/core-shell structure quantum dots or ZnSe:Cu+/ ZnS core/core-shell structure quantum dots, size
Within the scope of 1.5-10nm；
L) ZnSe/InP/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
M) PbS/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
N) PbSe/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
o)CuInS2The CuInS of quantum dot and core/shell structure2/ ZnS quantum dot, size is within the scope of 1.5-10nm；
P) CuS/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
q)AgInS2Quantum dot and AgInS2/ ZnS core-shell structured quantum dot, size is within the scope of 1.5-10nm
Preferably, the quantum dot includes having electroluminescent peak value within the scope of 380-450nm, and cadmium or mercury content are low
In the ZnSe/ZnSeS/ZnS quantum dots of 0.001% mass fraction；Electroluminescent peak value within the scope of 480-900nm, cadmium or
Mercury content less than the ZnTe/ZnSe/ZnS quantum dots of 0.001% mass fraction, ZnTe/ZnTeSe/ZnSe quantum dots or
ZnTe/ZnTeSe/ZnS quantum dots；For electroluminescent peak value within the scope of 500-700nm, cadmium or mercury content are less than 50%
CdSe/CdZnS/ZnS quantum dots or CdSe/CdZnSe/ZnSe/ZnS quantum dots.
Preferably, the molar ratio of quantum dot and energy transfer molecule is 100000:1 and 1:Between 100000.
It is another object of the present invention to provide the preparation methods of light-emitting diode assembly, include the following steps：
One substrate is provided, anode layer is set over the substrate；
Then hole transmission layer is set on the anode layer；
Then luminescent layer is set on the hole transport layer, the luminescent layer is that quantum dot is constituted with energy transfer molecule
Composite layer, one in following three steps of the preparation of the composite layer：
A) solution of the quantum dot is mixed with the solution of the energy transfer molecule；
B) powder of the quantum dot is dissolved into the solution of the energy transfer molecule；
C) solid of the energy transfer molecule or slurry are dissolved into the solution of the quantum dot；
Then electron transfer layer is set on the luminescent layer；
Finally cathode layer is set on the electron transfer layer.
It is another object of the present invention to provide a kind of display device, display device includes above-mentioned light emitting diode dress
It sets, visual information or tactile data can be exported, input information is used as by electric signal to operate, light emitting diode with quantum dots
Device can be used for the colored display of monochromatic, double-colored, three colors, four colors or more colors, wherein three colors show including bluish violet,
Green and red combination, or blue, green and red combination；Four colors are shown including hyacinthine, green, yellow and red
Combination.
Display device in the present invention includes the colour gamut of a covering multiple color, is more than national television system committee base
In 19762 ° of colour gamuts of International Commission on Illumination (CIE).
Beneficial effects of the present invention：The present invention is by the way that quantum dot to be simply dispersed in energy transfer molecule main body, energy
The high electronics of transfer of molecules and/or holoe carrier injectability increase the ability that quantum dot generates exciton, simultaneously because energy
The long alkyl chain that amount transfer of molecules has so that it can be combined with the ligand groups of quantum dot surface well, be more conducive to
Energy transfer process between quantum dot and energy transfer molecule is current quantum to obtain high electroluminescent efficiency
The injection of point hole/electronics provides a kind of new, effective method and thinking, and therefore, it is electric that the present invention can promote quantum dot
The performance of electroluminescence device.Further, good reality cadmium-free quantum dots or low cadmium quantum dot applied based on the present invention
It tests as a result, environmental-friendly QLED next-generation to development, quantum dot application and the commercialization of technology of quantum dots Related product have
It is significant.
Description of the drawings
Fig. 1 shows the multilayered structure schematic diagram of the QLED devices of the present invention；
Fig. 2 shows the exemplary chromatic value of 10 QLED devices proposed by the present invention and color；
Fig. 3 shows a kind of energy transfer molecule (2,7- bis- (diphenyl phosphine oxide) -9,9- in one embodiment of the invention
Octyl fluorenes, PO8) and three kinds of quantum dot solutions (the ZnSe/ZnSeS/ZnS quantum dots for the purple light that turns blue, CdSe/ of green light
CdZnS/ZnS quantum dots, and the CdSe/CdZnS/ZnS quantum dots that glow) absorption spectrum and photoluminescence spectra；
Fig. 4 shows the energy transfer process schematic diagram of running QLED in one embodiment of the invention.Hybrid layer packet
Include ZnSe/ZnSeS/ZnS quantum dots and energy transfer molecule PO8；
Fig. 5 shows the running multilayered structure having as illustrated in figure 1 c in one embodiment of the invention, and by measuring
Son point and energy transfer molecule composition hybrid layer QLED energy transfer process, energy transfer molecule can promote electronics and
Hole is injected into quantum dot；
Fig. 6 shows molecule class (a, b, c, d) and the oligomer/polymerization of energy transfer molecule in one embodiment of the invention
The exemplary construction of species (e)；
Fig. 7 shows the synthetic method of two exemplary energy transfer molecules (a) and (e) in Fig. 6；
Fig. 8 shows scanning electron microscope of the quantum dot under two different multiplying powers in one embodiment of the invention
Figure, in 9nm or so, PL peak wavelength exists the scale size of the ZnSe/ZnSeS/ZnS quantum dots with core shell/shell structure
440nm；
Fig. 9 shows the energy level embodiment of material used in the QLED in one embodiment of the invention；
Figure 10 shows the electroluminescent properties for the purple QLED that turns blue in one embodiment of the invention, and luminescent layer is by ZnSe/
ZnSeS/ZnS quantum dots and energy transfer molecule PO8 compositions；
Figure 11 show purple-light illuminanted QLED in one embodiment of the invention (a) J-V-I curves and (b) EQE and shine
Efficacy curve, luminescent layer are made of ZnSe/ZnSeS/ZnS quantum dots and energy transfer molecule PO8；
Figure 12 shows that the molar ratio of quantum dot and energy transfer molecule PO8 are to device performance in one embodiment of the invention
Influence, figure (a) and (b) are respectively that the light emission luminance of QLED built with ZnSe/ZnSeS/ZnS quantum dots and EQE contain with PO8
The influence of amount.
Figure 13 shows the stability of QLED devices in one embodiment of the invention, at pause switch working voltage 0-6v
Cycle 1200 times；
Figure 14 shows the song that the QLED devices of purple-light illuminanted ZnSe/ZnSeS/ZnS in one embodiment of the invention are stablized
Line；
Figure 15 shows the electroluminescent properties of the QLED of green light in one embodiment of the invention, luminescent layer point by
CdSe/CdZnS/ZnS quantum dots and energy transfer molecule PO8 compositions；
Figure 16 show the QLED of green light in one embodiment of the invention (a) J-V-I curves and (b) EQE and shine
Efficiency curve, luminescent layer are made of CdSe/CdZnS/ZnS quantum dots and energy transfer molecule PO8；
Figure 17 shows the electroluminescent properties of the QLED to glow in one embodiment of the invention, and luminescent layer is by CdSe/
CdZnS/ZnS quantum dots and energy transfer molecule PO8 compositions；
Figure 18 show the QLED to glow in one embodiment of the invention (a) J-V-I curves and (b) EQE and shine
Efficacy curve, luminescent layer are made of CdSe/CdZnS/ZnS quantum dots and energy transfer molecule PO8.
Identical component has used identical reference numeral in the accompanying drawings.Attached drawing only symbolically shows the reality of the application
Apply scheme.
Specific implementation mode
Below in conjunction with the application embodiment, technical solutions in the embodiments of the present application is described in detail.It answers
It is noted that described embodiment is only a part of embodiment of the application, rather than whole embodiments.
Fig. 1 illustrates the schematic diagram of the multilayered structure of the QLED devices in the embodiment of the present invention, includes successively from the bottom up
One anode, a hole transmission layer, the hybrid layer of a quantum dot and energy transfer molecule, an electron transfer layer, and
One cathode.
The anode material is used to connect the anode of external power, and in a specific embodiment, anode material is conduction
Metal oxide or conducting polymer, preferably indium tin oxide (ITO).The thickness of anode can be 10-1000nm, preferably
For 100-400nm.
In a preferred embodiment, anode surface is additionally provided with the conductive layer that can inject hole.It is specific at one
Embodiment in, conductive layer be preferably molar ratio be 5:1 poly- 3,4- ethylenedioxy thiophenes：Poly styrene sulfonate (PEDOT:
PSS coating PEDOT):The thickness of PSS coatings can be 5-100nm, preferred thickness 10-50nm.In a specific implementation
In example, conductive layer is arranged by way of spin coating on the anode.
Hole transmission layer is mainly used for effect of the transporting holes to luminescent layer.Hole transmission layer can be selected from point with the following group
One kind in son：Tertiary aromatic amine, thiophene oligomers, thiophen polymer, pyrroles's oligomer, vinyl penylene oligomer, vinyl benzene
It is oligomeric to support polymer, vinylcarbazole oligomer, vinylcarbazole polymer, fluorine oligomer, fluoropolymer, acetenyl penylene
Object, acetenyl polyphenylene polymer, penylene oligomer, polyphenylene polymer, oligomerization of acetylene object, acetylene polymer, phthalocyanine, phthalocyanine derive
Object, porphyrine and seaweed alkali derivant.In a specific embodiment, hole transmission layer is vinylcarbazole polymer
(PVK), hole transmission layer is arranged on the electrically conductive by way of spin coating, and the thickness of hole transmission layer can be 20-600nm,
Preferred thickness is 50-200nm.
The hybrid layer of quantum dot and energy transfer molecule is mainly used for shining, and it is to be located at hybrid layer or more due to coming to shine
Hole transmission layer and electron transfer layer in hole and electronics it is compound.According to the structure and work(of energy transfer molecule energy transfer
Can, there are three patterns for hybrid layer tool, as shown in fig. 1：A) energy transfer molecule is donator type, and electron injection can be promoted to amount
Sub- point；B) energy transfer molecule is receptor type, hole can be promoted to be injected into quantum dot；C) energy transfer molecule be donor-by
Build can promote electrons and holes simultaneously while be injected into quantum dot.Energy transfer molecule can be molecule class, oligomeric species
Or polymerization species.In one preferred embodiment, energy transfer molecule is easy to generate electronics or/and hole, and energy
Transfer of molecules have the band gap wider than quantum dot, meanwhile, the long alkyl chain that energy transfer molecule has can be very good with it is described
Quantum dot surface is combined, and is crosslinked by click chemistry.Electronics or/and hole vectors sub- point are resulted in upper type
Injection, to solve the problems, such as that exciton is not easy to be injected in quantum dot.In a preferred embodiment, quantum dot include with
One kind in the quantum dot of lower structure：
A) ZnSe/ZnSeS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
B) ZnTe/ZnSe/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
C) ZnTe/ZnTeS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
D) CdSe/CdZnS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
E) CdSe/CdZnSe/ZnSe/ZnS core shells/shell/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
F) CdTe/CdZnS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
G) CdS/ZnS core/shell structures, CdS/ZnSe/ZnS core shells/shell structure or CdZnS/ZnSe/ZnS core shells/shell
Structure quantum point, size is within the scope of 1.5-10nm；
H) CdTe/InP/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
I) InP/ZnS core/shell structures quantum dot, size is within the scope of 1.5-9nm；
J) additive Mn ZnSe:Mn2+/ ZnS core/core-shell structure quantum dots, ZnSe/ZnS:Mn2+/ ZnS core/shell/shell structure quantum
Point or ZnS:Mn2+/ ZnS core/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
K) Copper-cladding Aluminum Bar ZnS:Cu+/ ZnS core/core-shell structure quantum dots or ZnSe:Cu+/ ZnS core/core-shell structure quantum dots, size
Within the scope of 1.5-10nm；
L) ZnSe/InP/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
M) PbS/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
N) PbSe/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
o)CuInS2The CuInS of quantum dot and core/shell structure2/ ZnS quantum dot, size is within the scope of 1.5-10nm；
P) CuS/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
q)AgInS2Quantum dot and AgInS2/ ZnS core-shell structured quantum dot, size is within the scope of 1.5-10nm.
In a preferred embodiment, quantum dot include have electroluminescent peak value within the scope of 380-450nm, cadmium or
Person's mercury content is less than the ZnSe/ZnSeS/ZnS quantum dots of 0.001% mass fraction；Electroluminescent peak value is in 480-900nm ranges
Interior, cadmium or mercury content are less than ZnTe/ZnSe/ZnS quantum dots, the ZnTe/ZnTeSe/ZnSe quantum of 0.001% mass fraction
Point or ZnTe/ZnTeSe/ZnS quantum dots；Within the scope of 500-700nm, cadmium or mercury content are less than electroluminescent peak value
50% CdSe/CdZnS/ZnS quantum dots or CdSe/CdZnSe/ZnSe/ZnS quantum dots.In a specific embodiment
In, the preferred ZnSe/ZnSeS/ZnS quantum dots of quantum dot for the purple light that turns blue；The preferred CdSe/CdZnS/ of quantum dot of green light
ZnS quantum dot；The preferred CdSe/CdZnS/ZnS quantum dots of quantum dot to glow.
In a preferred embodiment, energy transfer molecule be molecule class, oligomeric species or polymerization species (Fig. 6 institutes
The molecular group shown or their derivative, (a)-(d) represents molecule class formation, (e) represents oligomer/polymer class in Fig. 6
Structure).In a preferred embodiment, energy transfer molecule have include in acetenyl or azido functional group one
Kind, it includes any one in acetenyl or azido the two that the ligand terminal groups of quantum dot, which have,；After Overheating Treatment, quantum
Point and energy transfer molecule completion are cross-linked to form composite layer.In a specific embodiment, energy transfer molecule PO8.
In one preferred embodiment, the molar ratio of quantum dot and energy transfer molecule is 100000:1 and 1:It is compound between 100000
One in following three steps of preparation of layer：
A) solution of quantum dot is mixed with the solution of energy transfer molecule；
B) powder of quantum dot is dissolved into the solution of energy transfer molecule；
C) solid of energy transfer molecule or slurry are dissolved into the solution of quantum dot.
In a specific embodiment, luminescent layer is arranged on the hole transport layer by spin coating mode, the thickness of luminescent layer
Degree can be 10-300nm, preferred thickness 40-100nm.
Electron transfer layer is mainly used for plaing a part of to transmit electronics to luminescent layer.Electron transfer layer is in following components
One kind：Furodiazole, oxadiazoles analog derivative, oxazole class, oxazole analog derivative, isoxazole, Isoxazole derivative, thiazole,
Thiazole, 1,2,3-triazoles, 1,2,3-triazoles derivative, 1,3,5-triazines class, 1,3,5-triazines class compound derivatives,
Quinoxaline, quinoxaline derivant, pyrroles's oligomer, azole polymer, vinyl penylene oligomer, vinyl polyphenylene polymer,
Vinylcarbazole oligomer, vinylcarbazole polymer, fluorine oligomer, fluoropolymer, acetenyl penylene oligomer, acetylenylbenzene
Support polymer, penylene oligomer, polyphenylene polymer, thiophene oligomers, thiophen polymer, oligomerization of acetylene object, acetylene polymer,
TiO2Nano particle, ZnO nano particle, SnO nano particles, gold nano grain and silver nano-grain.The thickness of electron transfer layer
Can be 20-600nm, preferably 50-200nm.In a specific embodiment, electron transfer layer is arranged by spin coating mode
On the light-emitting layer.
Cathode material is used to connect the cathode of external power.In a preferred embodiment, cathode material include Al, Ca,
Any one or more than one in Ba, Ca/Al, Ag.In a specific embodiment, cathode material Al.Cathode material
Thickness can be 10-600nm, preferred thickness 50-200nm.In a specific embodiment, cathode material is by steaming the side of crossing
Formula is set on electron transfer layer, cathode electrode layer thickness 200nm.
It should be understood that the manufacturing process of the embodiment of the present invention is related to above-mentioned anode, hole transmission layer, luminescent layer, electricity
Sub- transport layer, cathode specifically depositing operation can include but is not limited in spin coating, spraying, printing and vacuum evaporation
It is a kind of.
Fig. 2 shows the exemplary chromatic value of 10 QLED devices proposed in the embodiment of the present invention and color, and (white is small
Circle).Chromatic value and color show 4 bluish violet QLED, three green QLED and three red in 19762 ° of colour gamuts of CIE
QLED.The experimental results showed that, in 10 devices, the color of 9 QLED has exceeded the range (black of NTSC standard color in figure
Triangle).
In a more specifical embodiment, the material that primarily forms of anode is ITO, and conductive layer primarily forms material
For PEDOT:The material that primarily forms of PSS, hole transmission layer are PVK, and luminescent layer is ZnSe/ZnS nuclear shell structure quantum points and PO8
Composite layer, cathode primarily form material be Al.The energy level of light-emitting diode assembly in specific embodiment of the present invention
Structure is as shown in Figure 9.
Fig. 3 shows energy transfer molecule PO8 in a specific embodiment and three kinds of quantum dot solutions, and (turn blue purple light
ZnSe/ZnSeS/ZnS quantum dots, CdSe/CdZnS/ZnS quantum dots of green light, and the CdSe/CdZnS/ that glows
ZnS quantum dot) absorption spectrum and photoluminescence spectra.The absorbing wavelength of PO8 is within the scope of 270-330nm, and its is photic
Emission wavelength is within the scope of 310-400nm, in the absorption spectrum ranges that have entirely fallen in three kinds of quantum dots, this larger spectrum
Overlapping degree significantly increases the probability of energy transfer between energy transfer molecule and quantum dot, is the quantum yield of device
Provide reliable guarantee.
Fig. 4 shows the energy transfer process of running QLED in a specific embodiment, and hybrid layer includes in figure
ZnSe/ZnSeS/ZnS quantum dots, and it is wrapped in energy transfer molecule PO8.When QLED is run, PO8 molecules can be from cathode
Electronics is injected in layer, and is transmitted to similar quantum dot.Institute's injected electrons-hole is to foring an excitation state, and one
Thus a photon generates and launches.
Fig. 5 shows the running multilayered structure having as illustrated in figure 1 c, is turned by quantum dot and a specific energy
Move molecular composition hybrid layer QLED energy transfer process, energy transfer molecule shown in figure can promote simultaneously electronics and
Hole is injected into quantum dot.
(a) and (b) respectively illustrates the synthetic method of two exemplary energy transfer molecules (a) and (e) in Fig. 6 in Fig. 7.
(a) and (b) respectively illustrates scanning of the quantum dot under high magnification and low range in the embodiment of the present invention in Fig. 8
Electron microscope picture.In one embodiment, the scale size of the ZnSe/ZnSeS/ZnS quantum dots with core shell/shell structure
In 9nm or so.
Figure 10 shows the electroluminescent properties of the QLED for the purple light that turns blue in the embodiment of the present invention, luminescent layer by
ZnSe/ZnSeS/ZnS quantum dots and energy transfer molecule PO8 compositions.(a), (b) shows the bright royal purple of running equipment
The optical imagery of coloured light.(c) it is its corresponding electroluminescent spectrum, the result shows that, the emission peak wavelength of QLED exists in figure
440nm or so, and there is very sharp half-peak breadth (14.6nm).
Figure 11 shows purple-light illuminanted in specific embodiment of the present invention, and luminescent layer is by ZnSe/ZnSeS/ZnS quantum dots
With (a) J-V-I curves, (b) EQE and the luminous efficiency curve of the QLED of energy transfer molecule PO8 compositions.It can be seen that
Light emission luminance is 38cd/m2When, maximum EQE is 3.4%, maximum luminous efficiency 23lm/W.
Figure 12 shows in specific embodiment of the present invention, mole comparison device of quantum dot and energy transfer molecule PO8
The influence of performance, figure (a) and (b) be respectively the QLED built with ZnSe/ZnSeS/ZnS quantum dots light emission luminance and EQE with
The variation of PO8 contents, as it can be seen that (1 within the scope of certain mol proportion in figure:0-1:25), light emission luminance and EQE with quantum dot with
The increase of PO8 molecule molar ratios and obviously increase.
Figure 13 shows the stability of QLED devices in specific embodiment of the present invention, in figure as it can be seen that in intermittent duty electricity
It presses under 0-6v, after switch cycles 1200 times, the brightness of QLED can still keep good stability.
Figure 14 shows the curve that the QLED devices of purple-light illuminanted ZnSe/ZnSeS/ZnS in the embodiment of the present invention are stablized, real
Test the result shows that, in 10cd/m2Under light emission luminance, the half-life period of QLED is 133 hours.
Figure 15 shows the electroluminescent properties of the QLED of green-emitting in the embodiment of the present invention, and luminescent layer is by CdSe/
CdZnS/ZnS quantum dots and energy transfer molecule PO8 compositions.Figure (a) indicates electroluminescent hair when device is run under 6-14V voltages
Light spectrum, and (b) and (c) show running equipment bright green light optical imagery.
Figure 16 shows that (a) J-V-I curves, (b) EQE and luminous efficiency of the QLED of green light in the embodiment of the present invention is bent
Line, luminescent layer are made of CdSe/CdZnS/ZnS quantum dots and energy transfer molecule PO8, as it can be seen that its maximum luminousing brightness in figure
3800cd/m2。
Figure 17 shows the electroluminescent properties for the QLED that glows in the embodiment of the present invention, and luminescent layer is by CdSe/CdZnS/
ZnS quantum dot and energy transfer molecule PO8 compositions.(a) electroluminescent light when device is run under 6-16V voltages is represented
Spectrum, and (b) and (c) show running equipment bright red optical imagery.
Figure 18 shows that (a) J-V-I curves, (b) EQE and luminous efficiency of the QLED to glow in the embodiment of the present invention is bent
Line.Luminescent layer is made of CdSe/CdZnS/ZnS quantum dots and energy transfer molecule PO8.As it can be seen that maximum luminousing brightness is in figure
6300cd/m2, for corresponding wavelength at 625nm, maximum EQE is 0.63%, and corresponding light emission luminance is 68cd/m2Place.
Embodiment 1
The synthesis of P8 molecules：
Under argon atmosphere, bis- bromo- 9,9- dioctyl fluorenes of 3.29g (6mmol) 2,7- are dissolved into 80ml anhydrous tetrahydro furans
In, and cool to -78 DEG C (dry ice-propanone baths).Being slowly added dropwise 5.1ml n-BuLis, (2.5M is in hexane；
12.75mmol), thick bright yellow solution is obtained.20min is persistently stirred at -70 DEG C, is then lifted out reaction mixture
Temperature is to 0 DEG C.Temperature is risen into room temperature again, 2.8g (12.75mmol) chloride 2-phenyl-phosphine is added.In quenching for 2ml degassed methanols
Before going out, reactant is stirred to additional 3 hours at -70 DEG C.Decompression removal volatile matter, is left oil-based liquid.By crude material
Material purifying, by the column chromatography (Rf=0.29) of silica, with chloroform/n-hexane (2:8) it is used as mobile phase, is finally obtained
The pure P8 of 3.50g (77%) chemistry.
Embodiment 2
The synthesis of PO8 molecules：
The hydrogenperoxide steam generator of 3.03g (4mmol) P8,50ml dichloromethane and 10ml 30% are mixed, mixed under room temperature
It is stirred overnight.By organic layer separation, and washing and salt washing successively.Product is evaporated drying, obtains white solid, is passed through
It is recrystallized in toluene/n-hexane and is further purified, the pure PO8 of chemistry of 2.7g (85%) is finally obtained.
Embodiment 3
The pretreatment and cleaning of the ITO pieces of prepatterned：
The ITO chips that 12 surfaces are covered with the prepatterned of polymer are set on the glass substrate, are immersed in 80 DEG C
5min in 5% sodium hydrate aqueous solution.It repeats the above steps, then by chip nanopure water, 20% aqueous ethanolamine
Cleaning, and ultrasound 15min are then cleaned and are dried with sufficient nanopure water.Finally, that ITO chips are loaded to plasma is clear
Chamber wash, the equipment surface that ITO is coated are clean.
Embodiment 4
Pass through the ZnSe/ZnSeS/ZnS quantum dots of high quality, structure purple light QLED：
The device chip of the ITO coatings of precleaning, applies last layer conductive layer, and experimentation is：Using spin coating instrument, revolving
Rotary speed is 1750rpm, by 200 microlitres of molar ratios 5:1 PEDOT:PSS aqueous solutions are coated to its surface, rotational time
60s.Then device is dried in vacuo 20min in 180 DEG C of container, cools to room temperature, further coated on device another
Layer hole transport strata 4- butyl benzenes-benzidine (molecular weight>50,000), pass through 100 microlitres of 0.05% polymer of wt of utilization
Chlorobenzene dispersion liquid carries out spin coating, rotary speed 2500rpm, rotational time 60s.Then the vacuum tank by device at 160 DEG C
Middle dry 40min.Device is cooled down, and spin coating quantum dot hybrid layer and energy transfer molecule on it.Prepare quantum dot and energy
The process of mixture for measuring transfer of molecules is to be dissolved in the quantum dot purified in n-hexane/toluene, change concentration make its
The trap of 400nm is adjusted to about 1.0, and the energy transfer molecule of 0.01% mass fraction is then added in solution.Mixed solution
The process for being spin-coated on the surface of device piece is：100 microlitres of solution are added to chip surface, and in rotary speed 2000rpm speed
Under, spin coating 60 seconds is then 30 minutes dry under 140 DEG C of vacuum by chip, and cools to room temperature.Then by 2 × 10-
The cathode layer of 200nm thickness aluminium layers is deposited in the method for hot evaporation in the vacuum of 6 supports.Then device is closed, is wrapped in asphalt mixtures modified by epoxy resin
In fat, and the 10min under the radiation of a UV lamp.The electrical and optical properties of QLED, with KEITHLEY series work(more than 2400
For energy in charts and graphs (2.0 softwares of subsidiary LabTracer) to be tested in the system of energy source, an Ossila OLED/OPV test is flat
Platform, a NEWPORT 2835C multifunctional light cosmogony, with one calibration 818 optical detection probes of NEWPORT, gauge it is defeated
Go out and collected by 8.2 softwares of LabView, tests the QLED of light-emitting area 1.5mm × 3mm=4.5 × 10-6m2.
Embodiment 5
Pass through the CdSe/CdSeS/ZnS quantum dots of high quality, structure green light QLED：
The structure of green light CdSe/CdSeS/ZnS QLED is similar in above-described embodiment 4 purple-light illuminanted QLED, in addition to table
The ligand modified green light CdSe/CdSeS/ZnS quantum dots in face replace ZnSe/ZnSeS/ZnS quantum dots.
Embodiment 6
Pass through the CdSe/CdSeS/ZnS quantum dots of high quality, structure feux rouges QLED：
The structure of feux rouges CdSe/CdSeS/ZnS QLED is similar to purple-light illuminanted QLED in above-described embodiment 4, in addition to table
The ligand modified feux rouges CdSe/CdSeS/ZnS quantum dots in face replace ZnSe/ZnSeS/ZnS quantum dots.
Test result：
Based on no cadmium, surface modification has the dress of the ZnSe/ZnSeS/ZnS quantum dots of ligand and the QLED of energy transfer molecule
Performance is set, can be summarized as follows:
1) in the electroluminescence wavelength (Figure 10) of ultraviolet-purple light range 380nm-450nm.
2) maximum luminousing brightness 620cd/m2(Figure 11).
3) maximum luminous efficiency 23.22lm/W (Figure 11).
4) maximum EQE is 3.4%, maximum luminousing brightness 38cd/m2, emission peak 440nm.
5) emission peak has sharp line width (half-peak breadth=14.6nm) (Figure 10).
6) start voltage and there was only 2.8V (Figure 10).
7) holding time is more than 3 months.
8) when being tested under air and ambient enviroment, equipment half-life period is more than 130 hours.
9) after cycling on and off 1200 times, equipment is still stablized, and shows that emissive porwer does not have significant change (small
In 5% deviation).
10) luminescent color of Three Represents, 1976CIE L*a*b colour gamuts, chromatic value (0.242,0.051), (0.235,
, and (0.224,0.097) (Fig. 2) 0.075).
QLED based on CdSe/ZnS quantum dots and energy transfer molecule can be summarized as follows：
11) electroluminescent in the red range of the blueness-of visible light (480-700nm) wavelength.
12) maximum brightness of green light QLED reaches 3000cd/m2, emission peak is in 525nm.
13) maximum brightness of feux rouges QLED reaches 6300cd/m2, emission peak is in 625nm.
14) maximum luminous efficiency 4.57lm/W, light emission luminance is in 41.4cd/m2Place.
15) the opening voltage of feux rouges QLED is down to 1.9V, and the opening voltage of green light QLED is down to 2.2V.
16) maximum EQE is 0.7%, and light emission luminance is in 41.4cd/m2Place.
17) emission peak has sharp line width (half-peak breadth 24nm).
18) service life is preserved more than 6 months.
19) in air and ambient enviroment, equipment half-life period is more than 130 hours.
20) after cycling on and off 520 times, equipment is still stablized, and shows that emissive porwer does not have significant change
(deviation for being less than 5%).
21) the green luminescence color of Three Represents, 1976CIE L*a*b colour gamuts, chromatic value (0.102,0.558),
(0.092,0.560), and (0.088,0.562).
22) the red light-emitting color of Three Represents, 1976CIE L*a*b colour gamuts, chromatic value (0.478,0.521),
(0.482,0.524), and (0.484,0.525).
Although inventor has done more detailed elaboration to the technical solution of the application and has enumerated, it should be understood that for
For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious
, cannot all be detached from the essence of the application spirit, the term occurred in the application be used for elaboration to technical scheme and
Understand, the limitation to the application can not be constituted.
Claims (12)
1. a kind of light-emitting diode assembly, including：
A) hole transmission layer, for injection and transporting holes；
B) luminescent layer is contacted with the hole transmission layer；
C) electron transfer layer is contacted with the luminescent layer, for injecting and transmitting electronics to the luminescent layer；
D) anode and cathode is used for DC voltage, so that electric current is flowed in a device, and with ultraviolet light, visible light or near-infrared
The form of light sends out radiation, and the light-emitting diode assembly is made to shine；
It is characterized in that, the luminescent layer includes quantum dot and energy transfer molecule, the energy transfer molecule is as the amount
The decentralized medium of son point has high electronics and/or holoe carrier injectability, and passes through click chemistry with the quantum dot
It is crosslinked.
2. light-emitting diode assembly according to claim 1, which is characterized in that between the cathode and the anode
In addition when the DC voltage of 0-30V, the light-emitting diode assembly has electroluminescent of the wavelength within the scope of 380-900nm.
3. light-emitting diode assembly according to claim 1, which is characterized in that the energy transfer molecule has high fluorescence
Quantum efficiency, redox property reversible in nonaqueous electrolyte and the band gap wider than the quantum dot, to obtain height
The electronics and/or holoe carrier of effect inject.
4. light-emitting diode assembly according to claim 1, which is characterized in that the quantum dot and the energy transfer point
Son is cross-linked to form composite layer by click chemistry, wherein the energy transfer molecule includes in acetenyl or azido functional group
One kind, the ligand terminal groups of the quantum dot include any one in acetenyl or azido the two；After Overheating Treatment,
The quantum dot and energy transfer molecule completion are cross-linked to form composite layer.
5. light-emitting diode assembly according to claim 1, which is characterized in that the energy transfer molecule be molecule class,
Oligomeric species either polymerize species and include at least one of following molecular group or their derivative：
Wherein R1, R2, R3For-(CH2) x- (CH=CH) y- (CH2) z-R；R be following group in one kind-H ,-Cl ,-Br ,-
I、-OH、-OCH3、-OC2H5、-CHO、-COOCH3、-COOH、-CONH2、-COCl、-COBr、-COI、-NH2、-N+(CH3)3、-C
(CH3)3,-CH=CH2、-CCH、-C6H5、-C5H5、-N3、-OCN、-NCO、-CN、-NC、-NO2、-C5H4N、-SH、-S-S-H、-
SOCH3、-SO2H、-SCN、-NCS、-CSH、-PH2, phosphono, phosphate, guanyl-, cytimidine base, adenyl, thymus gland
Pyrimidine radicals.
6. light-emitting diode assembly according to claim 1, which is characterized in that the electron transfer layer includes with the following group
At least one of molecule：Furodiazole, oxadiazoles analog derivative, oxazole class, oxazole analog derivative, isoxazole, isoxazole spread out
Biology, thiazole, thiazole, 1,2,3-triazoles, 1,2,3-triazoles derivative, 1,3,5-triazines class, 1,3,5-triazines class
Close object derivative, quinoxaline, quinoxaline derivant, pyrroles's oligomer, azole polymer, vinyl penylene oligomer, vinyl
Polyphenylene polymer, vinylcarbazole oligomer, vinylcarbazole polymer, fluorine oligomer, fluoropolymer, acetenyl penylene are oligomeric
Object, acetenyl polyphenylene polymer, penylene oligomer, polyphenylene polymer, thiophene oligomers, thiophen polymer, oligomerization of acetylene object, second
Alkynes polymer, TiO2Nano particle, ZnO nano particle, SnO nano particles, gold nano grain and silver nano-grain.
7. light-emitting diode assembly according to claim 1, which is characterized in that the hole transmission layer includes with the following group
One kind in molecule：Tertiary aromatic amine, thiophene oligomers, thiophen polymer, pyrroles's oligomer, vinyl penylene oligomer, vinyl
Polyphenylene polymer, vinylcarbazole oligomer, vinylcarbazole polymer, fluorine oligomer, fluoropolymer, acetenyl penylene are oligomeric
Object, acetenyl polyphenylene polymer, penylene oligomer, polyphenylene polymer, oligomerization of acetylene object, acetylene polymer, phthalocyanine, phthalocyanine derive
Object, porphyrine and seaweed alkali derivant.
8. light-emitting diode assembly according to claim 1, which is characterized in that the quantum dot includes the amount with lower structure
One kind in son point：
A) ZnSe/ZnSeS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
B) ZnTe/ZnSe/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
C) ZnTe/ZnTeS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
D) CdSe/CdZnS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
E) CdSe/CdZnSe/ZnSe/ZnS core shells/shell/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
F) CdTe/CdZnS/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
G) CdS/ZnS core/shell structures, CdS/ZnSe/ZnS core shells/shell structure or CdZnS/ZnSe/ZnS core shells/shell structure
Quantum dot, size is within the scope of 1.5-10nm；
H) CdTe/InP/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
I) InP/ZnS core/shell structures quantum dot, size is within the scope of 1.5-9nm；
J) additive Mn ZnSe:Mn2+/ ZnS core/core-shell structure quantum dots, ZnSe/ZnS:Mn2+/ ZnS core/shell/core-shell structure quantum dots or
Person ZnS:Mn2+/ ZnS core/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
K) Copper-cladding Aluminum Bar ZnS:Cu+/ ZnS core/core-shell structure quantum dots or ZnSe:Cu+/ ZnS core/core-shell structure quantum dots, size exist
Within the scope of 1.5-10nm；
L) ZnSe/InP/ZnS core shells/core-shell structure quantum dots, size is within the scope of 1.5-9nm；
M) PbS/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
N) PbSe/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
o)CuInS2The CuInS of quantum dot and core/shell structure2/ ZnS quantum dot, size is within the scope of 1.5-10nm；
P) CuS/ZnS core/shell structures quantum dot, size is within the scope of 1.5-10nm；
q)AgInS2Quantum dot and AgInS2/ ZnS core-shell structured quantum dot, size is within the scope of 1.5-10nm.
9. light-emitting diode assembly according to claim 8, which is characterized in that the quantum dot includes having electroluminescent
For peak value within the scope of 380-450nm, cadmium or mercury content are less than the ZnSe/ZnSeS/ZnS quantum dots of 0.001% mass fraction；
For electroluminescent peak value within the scope of 480-900nm, cadmium or mercury content are less than the ZnTe/ZnSe/ZnS of 0.001% mass fraction
Quantum dot, ZnTe/ZnTeSe/ZnSe quantum dots or ZnTe/ZnTeSe/ZnS quantum dots；Electroluminescent peak value is in 500-
Within the scope of 700nm, cadmium either mercury content be less than 50% CdSe/CdZnS/ZnS quantum dots or CdSe/CdZnSe/ZnSe/
ZnS quantum dot.
10. light-emitting diode assembly according to claim 1, which is characterized in that quantum dot described in the luminescent layer with
The molar ratio of the energy transfer molecule is 100000:1 and 1:Between 100000.
11. a kind of preparation method of light-emitting diode assembly, includes the following steps：
One substrate is provided, anode layer is set over the substrate；
Then hole transmission layer is set on the anode layer；
Then luminescent layer is set on the hole transport layer, the luminescent layer is that quantum dot is answered with what energy transfer molecule was constituted
Close layer, one in following three steps of the preparation of the composite layer：
A) solution of the quantum dot is mixed with the solution of the energy transfer molecule；
B) powder of the quantum dot is dissolved into the solution of the energy transfer molecule；
C) solid of the energy transfer molecule or slurry are dissolved into the solution of the quantum dot；
Then electron transfer layer is set on the luminescent layer；
Finally cathode layer is set on the electron transfer layer.
12. a kind of electronic display unit can export visual information or tactile data, by electric signal be used as input information come
Operating, the electronic display unit include any light-emitting diode assembly, the light-emitting diodes in claim 1-10
Pipe device can be used for the colored display of monochromatic, double-colored, three colors, four colors or more colors, wherein three colors are shown including royal purple
The combination of color, green and red, or blue, green and red combination；Four colors show including hyacinthine, green, yellow and
Red combination.
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| CN110164947A (en) * | 2019-06-12 | 2019-08-23 | 京东方科技集团股份有限公司 | Array substrate and preparation method thereof, display panel |
| CN110164947B (en) * | 2019-06-12 | 2021-03-26 | 京东方科技集团股份有限公司 | Array substrate, preparation method thereof and display panel |
| WO2021111777A1 (en) * | 2019-12-02 | 2021-06-10 | 信越化学工業株式会社 | Quantum dot, wavelength conversion material, backlight unit, image display device, and method for manufacturing quantum dot |
| JPWO2021111777A1 (en) * | 2019-12-02 | 2021-06-10 | ||
| JP7273992B2 (en) | 2019-12-02 | 2023-05-15 | 信越化学工業株式会社 | Quantum dot, wavelength conversion material, backlight unit, image display device, and method for manufacturing quantum dot |
| WO2023070473A1 (en) * | 2021-10-28 | 2023-05-04 | 京东方科技集团股份有限公司 | Quantum dot light-emitting device and preparation method therefor, display substrate, and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108389982B (en) | 2020-03-27 |
| WO2018035948A1 (en) | 2018-03-01 |
| CN106356462A (en) | 2017-01-25 |
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