CN106803546A - A kind of light emitting diode with quantum dots and preparation method thereof - Google Patents
A kind of light emitting diode with quantum dots and preparation method thereof Download PDFInfo
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- CN106803546A CN106803546A CN201710088403.XA CN201710088403A CN106803546A CN 106803546 A CN106803546 A CN 106803546A CN 201710088403 A CN201710088403 A CN 201710088403A CN 106803546 A CN106803546 A CN 106803546A
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention provides a kind of light emitting diode with quantum dots, including anode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and the negative electrode for setting gradually, also including being arranged at the anode modification layer of the anode and hole injection layer；The anode modification layer includes fluorine-containing organic material.The light emitting diode with quantum dots that the present invention is provided, using fluorine-containing organic material as anode modification layer, is arranged between anode and hole injection layer, and fluoro substituents have played strong electron attraction with its extremely strong electronegativity, realizes the raising to hole injection；And the stable chemical nature of fluorine-containing organic material, can stablize the luminous efficiency for improving light emitting diode with quantum dots, increase the service life.
Description
Technical field
The present invention relates to light emitting diode with quantum dots technical field, more particularly to a kind of light emitting diode with quantum dots and its system
Preparation Method.
Background technology
Quantum dot is the nano material of quasi-zero dimension, is made up of a small amount of atom.Quantum dot belongs to inorganic semiconductor material, compared with
Organic material has more stable photochemical stability, and can be realized to fluorescence ripple by regulating and controlling the size of quantum dot
The long, regulation and control of emission spectrum, with excellent fluorescence quantum yield.Due to excellent characteristic, quantum dot is received significant attention, quilt
It is widely used in display technology field.
Light emitting diode with quantum dots (QLED) is a kind of with quantum dot as luminescent layer, can produce and send any visible wavelength
Light quantum dot organic luminescent device.Light emitting diode with quantum dots have high brightness, high-purity, low-power consumption, colour gamut wide, can be big
Area solution processes plurality of advantages.But current light emitting diode with quantum dots carrier injection is uneven, mainly hole injection
Speed be far smaller than electron injection speed, cause luminous efficiency not high, the problem of short life.
The content of the invention
It is an object of the invention to provide a kind of light emitting diode with quantum dots containing anode modification layer and preparation method thereof.This
Invent provide light-emitting diode luminous efficiency is high and good stability, increase the service life.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of light emitting diode with quantum dots, including anode, hole injection layer, the hole biography for setting gradually
Defeated layer, quantum dot light emitting layer, electron transfer layer and negative electrode, it is characterised in that also including being arranged at the anode and hole injection
The anode modification layer of layer；The anode modification layer includes fluorine-containing organic material.
Preferably, the anode modification layer includes one or more in fluorine-containing polyolefin；The thickness of the anode modification layer
It is 0.1~10nm to spend.
Preferably, the anode modification layer includes polytetrafluoroethylene (PTFE), Kynoar, fluorinated ethylene propylene copolymer, poly-
One or more in PVF, ethylene-tetrafluoroethylene copolymer and polytrifluorochloroethylene.
Preferably, the anode includes one or more in metal oxide, metal simple-substance and carbonaceous material；The sun
The thickness of pole is 100~250nm.
Preferably, the hole injection layer includes Polyglycolic acid fibre and poly styrene sulfonate；The hole injection
The thickness of layer is 10~100nm.
Preferably, the hole transmission layer polyvinylcarbazole, triphenyl diamine, triphenyl diamine polymer, it is poly- [(N, N '-
(4- n-butylphenyls)-N, N ' diphenyl-Isosorbide-5-Nitrae-phenylenediamines)-ALT- (9,9- di-n-octyl fluorenyl -2,7- diyls)], 4,4- bis-
In (9- carbazoles) biphenyl, TCTA trichlorothiolacetic acid and N, N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines
One or more；The thickness of the hole transmission layer is 10~100nm.
Preferably, the quantum dot light emitting layer includes core-shell quanta dots；The thickness of the quantum dot light emitting layer be 10~
100nm。
Preferably, the electron transfer layer includes zinc oxide and/or titanium dioxide；The thickness of the electron transfer layer is 10
~500nm.
Preferably, the negative electrode includes one or more in aluminium, silver, copper or calcium；The thickness of the negative electrode be 100~
200nm。
Present invention also offers the preparation method of the light emitting diode with quantum dots described in above-mentioned technical proposal, including following step
Suddenly：Anode modification layer, hole injection layer, hole transmission layer, quantum dot light emitting layer, electric transmission are sequentially depositing on the anode
Layer and negative electrode；The anode modification layer is deposited using vacuum thermal evaporation.
The light emitting diode with quantum dots that the present invention is provided, using fluorine-containing organic material as anode modification layer, is arranged at anode
And hole injection layer between, fluoro substituents have played strong electron attraction with its extremely strong electronegativity, realize noting hole
The raising for entering；And the stable chemical nature of fluorine-containing organic material, can stablize the luminous effect for improving light emitting diode with quantum dots
Rate, increases the service life；Fluorine-containing organic material has excellent insulating properties and ionization performance higher as anode modification layer, enters
And quenching of the excessive hole to exciton on anode is reduced, improve hole injection efficiency；Simultaneously using fluorine-containing organic material as sun
Pole decorative layer, with good film forming, improves the surface topography of anode layer, helps to reduce anode roughness so that anode
Layer uniform ground, reduces rough interfaces to the obstruction of carrier transport, significantly reduces note of the hole from anode to hole transmission layer
Enter energy barrier, improve hole injection efficiency, reduce driving voltage, and then improve the luminous efficiency of light emitting diode with quantum dots.In addition,
When the present invention is using fluorine-containing organic material as anode modification layer, good film-forming property, beneficial to the film forming of succeeding layer, between each layer of raising
Connectivity.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the schematic diagram of the light emitting diode with quantum dots that the embodiment of the present invention 1 is prepared；Wherein, 1- anodes, 2- sun
Pole decorative layer, 3- hole injection layers, 4- hole transmission layers, 5- quantum dot light emitting layers, 6- electron transfer layers, 7- negative electrodes；
Hole is from anode to sky in the light emitting diode with quantum dots that Fig. 2 is prepared for the embodiment of the present invention 1 and comparative example 1
The injection energy barrier schematic diagram of cave transport layer.
Specific embodiment
The invention provides a kind of light emitting diode with quantum dots, including anode, hole injection layer, the hole biography for setting gradually
Defeated layer, quantum dot light emitting layer, electron transfer layer and negative electrode, also including being arranged at the anode modification of the anode and hole injection layer
Layer；The anode modification layer includes fluorine-containing organic material.
The light emitting diode with quantum dots that the present invention is provided, using fluorine-containing organic material as anode modification layer, is arranged at anode
And hole injection layer between, fluoro substituents have played strong electron attraction with its extremely strong electronegativity, realize noting hole
The raising for entering；And the stable chemical nature of fluorine-containing organic material, can stablize the luminous effect for improving light emitting diode with quantum dots
Rate, increases the service life；Fluorine-containing organic material has excellent insulating properties and ionization performance higher as anode modification layer, enters
And quenching of the excessive hole to exciton on anode is reduced, improve hole injection efficiency.
The light emitting diode with quantum dots that the present invention is provided includes anode.In the present invention, the anode preferably includes metal
One or more in oxide, metal simple-substance and carbonaceous material.In the present invention, the metal oxide preferably includes oxidation
One or more in indium tin, fluorine doped tin oxide and Al-Doped ZnO；The metal simple-substance preferably includes metal nanometer line or gold
Category net (metal mesh), more preferably including nano silver wire, nanowires of gold, copper nano-wire, cupro-nickel wire netting, gold nano metal
One or more in net, copper nano metal net；The carbonaceous material preferably includes Graphene, CNT and carbon nanocoils
In one or more.The present invention does not have special wanting to the specific source of the metal oxide, metal simple-substance and carbonaceous material
Ask, using well-known to those skilled in the art；In an embodiment of the present invention, the anode specifically uses commercially available ITO
Electro-conductive glass.
In the present invention, the thickness of the anode is preferably 100~250nm, more preferably 120~200nm, more excellent
Elect 150~180nm as.
The light emitting diode with quantum dots that the present invention is provided includes hole injection layer.In the present invention, the anode hole note
Enter layer and preferably include Polyglycolic acid fibre (PEDOT) and poly styrene sulfonate (PSS).In the present invention, the poly- ethylene
The mol ratio of dioxy thiophene and poly styrene sulfonate is preferably (1~5):(5~100), more preferably (2~3):(20~
80), most preferably 2:35~65.
In the present invention, the thickness of the hole injection layer is preferably 10~100nm, more preferably 15~90nm,
More preferably 30~60nm, most preferably 50nm.
The light emitting diode with quantum dots that the present invention is provided includes the anode being arranged between the anode and hole injection layer
Decorative layer.In the present invention, the anode modification layer includes fluorine-containing organic material, the one kind or many in preferably fluorine-containing polyolefin
Plant, more preferably polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), fluorinated ethylene propylene copolymer (FEP), poly- fluorine
One or more in ethene (PVF), ethylene-tetrafluoroethylene copolymer (ETFE) and polytrifluorochloroethylene (PCTFE).The present invention
To the no particular/special requirement in specifically source of the fluorine-containing organic material, using well-known to those skilled in the art.
In the present invention, the thickness of the anode modification layer is preferably 0.1~10nm, more preferably 0.5~8nm,
More preferably 2~6nm, most preferably 3~4nm.
The light emitting diode with quantum dots that the present invention is provided includes the hole transmission layer being arranged on the hole injection layer.
In the present invention, the hole transmission layer preferably includes polyvinylcarbazole (PVK), triphenyl diamine (TPD), triphenyl diamine polymerization
Thing (poly-TPD), poly- [(N, N '-(4- n-butylphenyls)-N, N ' diphenyl -1,4- phenylenediamines)-ALT- (9,9- di-n-octyls
Fluorenyl -2,7- diyls)] (TFB), 4,4- bis- (9- carbazoles) biphenyl (CBP), TCTA trichlorothiolacetic acid (TCTA) and N, N'- diphenyl -
One or more in N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines (NPB).The present invention is to the hole transmission layer
Specifically originate no particular/special requirement, using well-known to those skilled in the art.
In the present invention, the thickness of the hole transmission layer is preferably 10~100nm, more preferably 15~90nm,
More preferably 30~60nm, most preferably 50nm.
In the present invention, the PEDOT and PSS compoundings have excellent electric conductivity, can realize being passed with the hole
The level-density parameter of defeated layer, and then it is favorably improved hole transport efficiency；When using poly-TPD as hole transmission layer, poly-
TPD is with its excellent hole transport speed so that electron hole injection reaches balance.
The light emitting diode with quantum dots that the present invention is provided includes setting quantum dot light emitting layer on the hole transport layer.
In the present invention, the quantum dot light emitting layer preferably includes core-shell quanta dots.In the present invention, the core-shell quanta dots preferably have
There are core shell structure, including nucleome and the shell being coated on outside the nucleome.In the present invention, the component of the nucleome and shell is only
The A races of II B- VI or the B races of III B- V are on the spot selected from, quantum efficiency is improved.In the present invention, the component independence of the nucleome and shell
Ground is preferably one or more of ZnS, CdSe, HgTe, ZnSe, HgSe, CdS, ScNb and YNb.In an embodiment of the present invention,
The core-shell quanta dots are specially CdS/CdSe, CdSe/CdS, CdSe/ZnS or ZnS/CdSe.In the present invention, the nucleocapsid
Quantum dot is preferably green, red or blue core-shell quanta dots.The present invention does not have to the specific source of the quantum dot light emitting layer
Particular/special requirement, using quantum dot light emitting layer well-known to those skilled in the art.
In the present invention, the thickness of the quantum dot light emitting layer is preferably 10~100nm, more preferably 15~
50nm, more preferably 20~40nm.
The light emitting diode with quantum dots that the present invention is provided includes the electron transfer layer being arranged on the quantum dot light emitting layer.
In the present invention, the electron transfer layer preferably includes zinc oxide and/or titanium dioxide；In the present invention, the zinc oxide is excellent
Elect nano zine oxide as, the titanium dioxide is preferably nano titanium oxide；The particle diameter independence of the zinc oxide and titanium dioxide
Ground is preferably 10~90nm, more preferably 30~50nm.The present invention does not have to the source of the zinc oxide or titanium dioxide
Particular/special requirement, using zinc oxide well-known to those skilled in the art or titanium dioxide.When the electron transfer layer includes
When zinc oxide and titanium dioxide, the mass ratio of the zinc oxide and titanium oxide is preferably (1~2)：(2~4), more preferably
1.5：4.
In the present invention, the thickness of the electron transfer layer is preferably 10~500nm, more preferably 30~200nm,
More preferably 50~100nm.
The light emitting diode with quantum dots that the present invention is provided includes the negative electrode being arranged in the electronics point transport layer.In this hair
In bright, the negative electrode preferably includes one or more in aluminium, silver, copper and calcium；In the present invention, the negative electrode is further preferred
It is silver-colored calcium alloy or aerdentalloy；When negative electrode is using in the form of alloy when, content of the present invention to different component in the alloy
There is no particular/special requirement, using respective alloy well-known to those skilled in the art.
In the present invention, the thickness of the negative electrode is preferably 100~200nm, more preferably 130~190nm, more excellent
Elect 160~180nm as.
Present invention also offers the preparation method of the light emitting diode with quantum dots described in above-mentioned technical proposal, including following step
Suddenly：Anode modification layer, hole injection layer, hole transmission layer, quantum dot light emitting layer, electric transmission are sequentially depositing on the anode
Layer and negative electrode；The anode modification layer is deposited using vacuum thermal evaporation.
In the present invention, the hole injection layer, hole transmission layer, quantum dot light emitting layer and electron transfer layer are preferably with rotation
The mode of painting is deposited.
Present invention vacuum thermal evaporation anode modification layer on the anode.In the present invention, the vacuum of the evaporation is excellent
Elect 5 × 10 as-5~4 × 10-4Pa, more preferably 6~8 × 10-5Pa；In the present invention, the temperature of the evaporation is preferably
150~500 DEG C, more preferably more preferably 200~400 DEG C, 250~350 DEG C.
After obtaining the anode modification layer, present invention spin coating hole injection layer preferably in the anode modification layer.At this
In invention, the hole injection layer is preferably entered with the alcohol solutions of Polyglycolic acid fibre and poly styrene sulfonate mixture
Row spin coating.In the present invention, the spin coating of the hole injection layer is preferably carried out under an inert atmosphere；In the present invention, it is described poly-
The concentration of ethylenedioxy thiophene and poly styrene sulfonate in alcoholic solution is preferably 10~50mol/L, more preferably 15
~45mol/L.In the present invention, the speed of the spin coating is preferably 2000-6000r/s, more preferably 3000-5500r/
S, more preferably 4000-5000r/s；In the present invention, the time of the spin coating be preferably 40~60s, more preferably 50-60s.
After completing the spin coating of the hole injection layer, the present invention is preferably dried, and obtains the hole injection layer.At this
In invention, the dry time is preferably 15~30min, more preferably more preferably 20~25min, 22~24min；
In the present invention, the dry temperature is preferably 100~200 DEG C, more preferably 130~180 DEG C, more preferably 140
~160 DEG C.
After obtaining the hole injection layer, present invention spin coating hole transmission layer preferably on the hole injection layer.At this
In invention, the hole transmission layer is preferably carried out in a vacuum or inert atmosphere.In the present invention, the hole transmission layer is preferred
With polyvinylcarbazole, triphenyl diamine, triphenyl diamine polymer, it is poly- [(N, N '-(4- n-butylphenyls)-N, N ' diphenyl-
Isosorbide-5-Nitrae-phenylenediamine)-ALT- (9,9- di-n-octyl fluorenyl -2,7- diyls)] (TFB), 4,4- bis- (9- carbazoles) biphenyl, trichlorine be thio
The acetone soln form spin coating of acetic acid or N, N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines (NPB)；
In the present invention, the polyvinylcarbazole, triphenyl diamine, triphenyl diamine polymer, it is poly- [(N, N '-(4- n-butylphenyls)-
N, N ' diphenyl-Isosorbide-5-Nitrae-phenylenediamine)-ALT- (9,9- di-n-octyl fluorenyl -2,7- diyls)] (TFB), 4,4- bis- (9- carbazoles) connection
The chlorobenzene solution of benzene, TCTA trichlorothiolacetic acid or N, N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines (NPB)
Concentration be preferably 6~20mg/ml, more preferably more preferably 8~15mg/ml, 8~12mg/ml；In the present invention,
The speed of the spin coating is preferably 1500~4000r/s, more preferably more preferably 2000-3500r/s, 2500-
3000r/s；In the present invention, the time of the spin coating be preferably 20~50s, more preferably 25~40s.
After completing the spin coating of the hole transmission layer, the present invention is preferably dried, and obtains the hole transmission layer.At this
In invention, the dry time is preferably 15~30min, more preferably more preferably 20~25min, 22~24min；
In the present invention, the dry temperature is preferably 100~150 DEG C, more preferably 110~140 DEG C, more preferably 120
~130 DEG C.
After obtaining the hole transmission layer, the present invention preferably spin coating quantum dot light emitting layer on the hole transport layer.
In the present invention, the spin coating of the quantum dot light emitting layer is preferably carried out in a vacuum or inert atmosphere.In the present invention, it is described
Quantum dot light emitting layer is preferably with the acetone soln form spin coating of core-shell quanta dots.In the present invention, the core-shell quanta dots are being just
Concentration in octane solution is preferably 10~20mg/ml, more preferably more preferably 12~18mg/ml, 15~16mg/
ml.In the present invention, the speed of the spin coating is preferably 1500~4000r/s, more preferably 2000~3000r/s, more
Preferably 2500~3000r/s；In the present invention, the time of the spin coating be preferably 20~60s, more preferably 30~
55s, more preferably 40~50s.
After completing the spin coating of the quantum dot light emitting layer, the present invention is preferably dried, and obtains the quantum dot light emitting layer.
In the present invention, the dry time be preferably 5~10min, more preferably 6~8min；In the present invention, it is described dry
Dry temperature is preferably 150~250 DEG C, more preferably more preferably 170~220 DEG C, 190~200 DEG C.The present invention is with height
The warm fast mode for applying completes the spin coating of the quantum dot light emitting layer, is favorably improved the flatness of quantum dot light emitting layer.
After obtaining the quantum dot light emitting layer, present invention spin coating electron transfer layer preferably on the quantum dot light emitting layer.
In the present invention, the spin coating of the electron transfer layer is preferably carried out under vacuum or inert gas shielding.In the present invention, it is described
Electron transfer layer is preferably with the alcohol solutions spin coating of zinc oxide or titanium dioxide.In the present invention, the zinc oxide or dioxy
Change concentration of the titanium in alcoholic solution and be preferably 15~50mg/ml, more preferably 20~30mg/ml.In the present invention, it is described
The speed of spin coating is preferably 800~3000r/s, more preferably more preferably 1000~2500r/s, 1500~2000r/s；
In the present invention, the time of the spin coating be preferably 10~100s, more preferably more preferably 20~80s, 50~60s.
After completing the spin coating of the electron transfer layer, the present invention is preferably dried, and obtains the electron transfer layer.At this
In invention, the dry time is preferably 5~20min, more preferably more preferably 10~18min, 16~17min；
In the present invention, the dry temperature is preferably 100~300 DEG C, more preferably 150~250 DEG C, most preferably 200
℃。
After obtaining the electron transfer layer, the present invention obtains quantum preferably in the electric transmission layer surface evaporation cathode
Point luminescent diode.In the present invention, the vacuum of the evaporation is preferably 1~9 × 10-5Pa, more preferably 6~8 ×
10-5Pa；In the present invention, the temperature of the evaporation is preferably 500~1500 DEG C, more preferably 700~1300 DEG C, more excellent
Elect 800~1100 DEG C as.
In order to further illustrate the present invention, with reference to the quantum dot containing anode modification layer that embodiment is provided the present invention
Light emitting diode and preparation method thereof is described in detail, but they can not be interpreted as the limit to the scope of the present invention
It is fixed.
Embodiment 1:
It is 5 × 10 in vacuum-5Pa, temperature be 300 DEG C under the conditions of, thickness be 100nm indium-tin oxide anodes on be deposited with
Polytetrafluoroethylene (PTFE) anode modification layer, the thickness of anode modification layer is 4nm；
Following spin coating process is in the inert atmosphere (O of glove box2<1ppm,H2O<1ppm) under carry out：
Polyglycolic acid fibre and poly styrene sulfonate are with 1:5 mixed in molar ratio, prepares according to the concentration of 10mol/L
Methanol solution, with the speed spin coating 50s of 6000r/s in anode modification layer, then dries 30min under the conditions of 150 DEG C, obtains
Thickness is the hole injection layer of 20nm；
In the chlorobenzene solution of the PVK of hole injection layer surface spin coating 10mg/mL, according to the speed spin coating 40s of 3000r/s,
It is put at 120 DEG C of vacuum drying chamber and dries 20min, obtains the hole transmission layer that thickness is 30nm；
In the normal octane solution of the CdSe/CdS core-shell quanta dots of hole transport layer surface spin coating 15mg/mL, with 2500r/s
Speed spin coating 50s, 200 DEG C dry 10min, obtain thickness be 40nm quantum dot light emitting layer；
It is the ethanol solution of the Zinc oxide particles of 20nm in the particle diameter of quantum dot light emitting layer surface spin coating 20mg/mL, with
The speed spin coating of 2000r/s 40 seconds, then dries 20min at 100 DEG C, obtains the electron transfer layer that thickness is 50nm；
It is 9 × 10 in vacuum-5Pa, temperature is at 1000 DEG C, silver cathode to be deposited with electric transmission layer surface, and negative electrode is extremely thick
It is 100nm to spend, and obtains the light emitting diode with quantum dots containing anode modification layer.
The structural representation of the light emitting diode with quantum dots for preparing is as shown in Figure 1.
The hole of the light emitting diode with quantum dots containing anode modification layer for preparing is from anode to hole transmission layer
Inject the schematic diagram of energy barrier as shown in right in Figure 2：On the one hand, fluorine-containing organic material is used as anode modification layer, with splendid
Insulating properties, can reduce the ionization of anode layer, so that reduce left figure solid line in the work function such as Fig. 2 of anode will be apparently higher than the right side
Figure, reduces the injection energy barrier in hole；On the other hand, in the case of 0.1~1.0nm is very thin, hole is enough to tunnel injection, and
There is larger electrical potential difference between fluorine-containing organic material and hole transmission layer, further promote the injection in hole.
Embodiment 2:
It is 4 × 10 in vacuum-5Pa, temperature be 250 DEG C under the conditions of, thickness be 200nm nano silver wire anodes on be deposited with
Ethylene-tetrafluoroethylene copolymer anode modification layer, the thickness of anode modification layer is 6nm；
Following spin coating process is in the inert atmosphere (O of glove box2<1ppm,H2O<1ppm) under carry out：
Polyglycolic acid fibre and poly styrene sulfonate are with 20:80 mixed in molar ratio, according to the concentration system of 50mol/L
Standby ethanol solution, with the speed spin coating 60s of 7000r/s in anode modification layer, then dries 25min under the conditions of 150 DEG C, obtains
It is the hole injection layer of 30nm to thickness；
In the chlorobenzene solution of the poly-TPD of hole injection layer surface spin coating 8mg/mL, according to the speed spin coating of 2500r/s
40s, is put at 150 DEG C of vacuum drying chamber and toasts 10min, obtains the hole transmission layer that thickness is 20nm；
In the normal octane solution of the CdSe/CdS core-shell quanta dots of hole transport layer surface spin coating 18mg/mL, with 3000r/s
Speed spin coating 50 seconds, dry 5min at 250 DEG C, obtain the quantum dot light emitting layer that thickness is 30nm；
It is the ethanol solution of the titanium dioxide granule of 100nm in the particle diameter of quantum dot light emitting layer surface spin coating 20mg/mL, with
The speed spin coating of 3000r/s 60 seconds, then dries 10min at 300 DEG C, obtains the electron transfer layer that thickness is 60nm；
It is 5 × 10 in vacuum-5Pa, temperature is at 1000 DEG C, in electric transmission layer surface AM aluminum metallization negative electrode, negative electrode is extremely thick
It is 100nm to spend, and obtains the light emitting diode with quantum dots containing anode modification layer.
Comparative example 1
Following spin coating process is in the inert atmosphere (O of glove box2<1ppm,H2O<1ppm) under carry out：
Polyglycolic acid fibre and poly styrene sulfonate are with 1:5 mixed in molar ratio, prepares according to the concentration of 10mol/L
Methanol solution, with the speed spin coating 50s of 6000r/s in anode modification layer, then dries 30min under the conditions of 150 DEG C, obtains
Thickness is the hole injection layer of 20nm；
In the chlorobenzene solution of the PVK of hole injection layer surface spin coating 10mg/mL, according to the speed spin coating 40s of 3000r/s,
It is put at 120 DEG C of vacuum drying chamber and dries 20min, obtains the hole transmission layer that thickness is 30nm；
In the normal octane solution of the CdSe/CdS core-shell quanta dots of hole transport layer surface spin coating 15mg/mL, with 2500r/s
Speed spin coating 50s, 200 DEG C dry 10min, obtain thickness be 40nm quantum dot light emitting layer；
It is the ethanol solution of the Zinc oxide particles of 20nm in the particle diameter of quantum dot light emitting layer surface spin coating 20mg/mL, with
The speed spin coating of 2000r/s 40 seconds, then dries 20min at 100 DEG C, obtains the electron transfer layer that thickness is 50nm；
It is 9 × 10 in vacuum-5Pa, temperature is at 1000 DEG C, silver cathode to be deposited with electric transmission layer surface, and negative electrode is extremely thick
It is 100nm to spend, and obtains the light emitting diode with quantum dots without anode modification layer.
The hole of the light emitting diode with quantum dots without anode modification layer for preparing is from anode to hole transmission layer
Inject the schematic diagram of energy barrier as shown in left in Figure 2.
The above is only the preferred embodiment of the present invention, and any formal limitation is not made to the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of light emitting diode with quantum dots, including anode, hole injection layer, hole transmission layer, the quantum dot hair for setting gradually
Photosphere, electron transfer layer and negative electrode, it is characterised in that also the anode including being arranged between the anode and hole injection layer is repaiied
Decorations layer；The material of the anode modification layer includes fluorine-containing organic material.
2. light emitting diode with quantum dots according to claim 1, it is characterised in that the anode modification layer includes fluorine-containing poly-
One or more in alkene；The thickness of the anode modification layer is 0.1~10nm.
3. light emitting diode with quantum dots according to claim 2, it is characterised in that the anode modification layer includes polytetrafluoro
Ethene, Kynoar, fluorinated ethylene propylene copolymer, polyvinyl fluoride, ethylene-tetrafluoroethylene copolymer and polytrifluorochloroethylene
In one or more.
4. light emitting diode with quantum dots according to claim 1, it is characterised in that the anode include metal oxide,
One or more in metal simple-substance and carbonaceous material；The thickness of the anode is 100~250nm.
5. light emitting diode with quantum dots according to claim 1, it is characterised in that the hole injection layer includes poly- ethylene
Dioxy thiophene and poly styrene sulfonate；The thickness of the hole injection layer is 10~100nm.
6. light emitting diode with quantum dots according to claim 1, it is characterised in that the hole transmission layer includes polyethylene
Carbazole, triphenyl diamine, triphenyl diamine polymer, it is poly- [(N, N '-(4- n-butylphenyls)-N, N ' diphenyl -1,4- benzene two
Amine)-ALT- (9,9- di-n-octyl fluorenyl -2,7- diyls)], 4,4- bis- (9- carbazoles) biphenyl, TCTA trichlorothiolacetic acid and N, N'- bis-
One or more in phenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines；The thickness of the hole transmission layer is 10
~100nm.
7. light emitting diode with quantum dots according to claim 1, it is characterised in that the quantum dot light emitting layer includes nucleocapsid
Quantum dot；The thickness of the quantum dot light emitting layer is 10~100nm.
8. light emitting diode with quantum dots according to claim 1, it is characterised in that the electron transfer layer includes zinc oxide
And/or titanium dioxide；The thickness of the electron transfer layer is 10~500nm.
9. light emitting diode with quantum dots according to claim 1, it is characterised in that the negative electrode includes aluminium, silver, copper and calcium
In one or more；The thickness of the negative electrode is 100~200nm.
10. the preparation method of the light emitting diode with quantum dots described in any one of claim 1~9, comprises the following steps：Described
Anode modification layer, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and negative electrode are sequentially depositing on anode；
The anode modification layer is deposited using vacuum thermal evaporation.
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Application publication date: 20170606 |