CN107706315A - 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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- CN107706315A CN107706315A CN201710736808.XA CN201710736808A CN107706315A CN 107706315 A CN107706315 A CN 107706315A CN 201710736808 A CN201710736808 A CN 201710736808A CN 107706315 A CN107706315 A CN 107706315A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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Abstract
The invention provides a kind of light emitting diode with quantum dots and preparation method thereof, the present invention by including adulterate a small amount of vanadium molybdenum trioxide organic solution including the organic solution of triphenyl diamine polymer including the organic solution of quantum dot and organic solution including zinc oxide by sol evenning machine spin coating method sequentially in conductive substrates spin-coating film, obtain primary light emitting diode with quantum dots；Superficial deposit aluminium electrode in the obtained light emitting diode with quantum dots nonconductive matrix bottom side, obtains light emitting diode with quantum dots.The present invention realizes the raising of light emitting diode with quantum dots luminous efficiency using the molybdenum trioxide solution for adulterating a small amount of vanadium as hole injection layer；And the molybdenum trioxide solution of a small amount of vanadium of doping used in the present invention compares traditional hole injection layer material as hole injection layer（The mixed organic solvents of Polyglycolic acid fibre and poly styrene sulfonate）, there is the features such as cheap, light transmittance is more preferable.
Description
Technical field
The present invention relates to LED technology field, more particularly to a kind of light emitting diode with quantum dots and its preparation side
Method.
Background technology
Quantum dot（Quantum dots, QDs）, also known as semiconductor nano, refer to size in the dimension of three, space
The meter Sized Materials formed in nanometer scale or by them as elementary cell.Its emission spectrum can pass through change
QDs size controls, and by the size and its chemical composition that change QDs it can be made to launch light covering whole visible
Light area.Meanwhile QDs has good stability, long-time observation can be carried out to the object of mark, can apply to biology；
With larger stoke shift, be advantageous to the detection of fluorescence spectrum signal；Good biocompatibility, it can apply to biological living mark
Note and detection.Relative to the expensive manufacture craft of inorganic semiconductor material, it can be processed QDs materials with solution, pass through drop coating, rotation
The plain mode such as painting or printing carrys out film forming, enormously simplify the preparation technology of semiconductor devices, reduces production cost, in addition QDs
It is high with luminous efficiency, the good property of stability, there is great potential in display field.
Light emitting diode with quantum dots（Quantum dot light emitting diode, QLED）It is that one kind is made with QDs
For the electroluminescent device of luminescent layer, made simply because it has, small volume is of good quality, energy-conservation, the spy such as purity height of light
Point, by people's extensive concern.General QLED structures are made up of anode, hole transmission layer, QDs layers, electron transfer layer, negative electrode, together
When, in order to lift device performance, also usually add some functional layers, such as electron injecting layer, hole injection layer etc..
The content of the invention
It is an object of the invention to provide a kind of light emitting diode with quantum dots and preparation method thereof.Preparation provided by the invention
Method, method is simple and can realize that large area produces.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：The invention provides a kind of quantum dot hair
The preparation method of optical diode, comprises the following steps：
（1）By including adulterate the molybdenum trioxide organic solution of a small amount of vanadium including the organic solution of triphenyl diamine polymer including
The organic solution of quantum dot and organic solution including zinc oxide by inkjet printing methods sequentially in conductive substrates printout surface,
Obtain primary light emitting diode with quantum dots；
The molybdenum trioxide of molybdenum trioxide solution and the mass ratio of vanadium of a small amount of vanadium of doping are 1：（0.01~0.1）, solute is with having
Solvent mass ratio is（1~5）：100；
The quality of triphenyl diamine polymer and the volume ratio of organic solvent in the organic solution of the triphenyl diamine polymer
For（5~10）mg：（1~2）mL；
The quality of quantum dot and the volume ratio of organic solvent are in the organic solution of the quantum dot（5~25）mg：（1~2）mL；
The quality of zinc oxide and the volume ratio of organic solvent are in the organic solution including zinc oxide（10~20）mg：（1~3）
mL；
（2）In the step（1）The superficial deposit electrode of the bottom side at obtained primary light emitting diode with quantum dots nonconductive matrix bottom,
Obtain light emitting diode with quantum dots.
Preferably, organic solvent includes ethanol, methanol, benzene first in the molybdenum trioxide organic solution of a small amount of vanadium of doping
One in alcohol, ethylene glycol, n-butanol, isobutanol, neopentyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol and lauryl alcohol
Kind is a variety of.
Preferably, organic solvent includes chlorobenzene, toluene, two in the organic solution including triphenyl diamine polymer
It is one or more in toluene, styrene, chloroform and benzene.
Preferably, in the organic solution including quantum dot organic solvent include n-hexane, normal heptane, octane, decane,
One or more in hendecane, dodecane, n-tetradecane, hexadecane and n-octadecane.
Preferably, in the organic solution including zinc oxide organic solvent include ethanol, methanol, phenmethylol, ethylene glycol,
One or more in n-butanol, isobutanol, neopentyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol and lauryl alcohol.
Preferably, the step（1）Include adulterating the molybdenum trioxide organic solution of a small amount of vanadium including triphenyl diamine gathers
The organic solution of compound including the volume ratio of the organic solution of quantum dot and the organic solution including zinc oxide are 1:1:1:1.
Preferably, the step（1）In each solution independently also include adjust adhesive aggregation compound, it is described tune viscosity polymer include
One or more in polyethylene, polypropylene, polyvinyl chloride and polystyrene.
Preferably, the step（1）In the Solute mass of low quality in corresponding solution of adhesive aggregation compound is adjusted in each solution
0.05%.
Present invention also offers the light emitting diode with quantum dots that preparation method described in above-mentioned technical proposal obtains, including successively
Conductive substrates, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and the negative electrode of setting；The hole note
Enter the blended organic solution of layer to obtain through sol evenning machine spin coating；Including triphenyl diamine polymer described in the hole transmission layer warp
Organic solution obtains through sol evenning machine spin coating；The quantum dot light emitting layer warp organic solution including quantum dot is revolved through sol evenning machine
Painting obtains；The electron transfer layer warp organic solution including zinc oxide obtains through sol evenning machine spin coating.
Preferably, the conductive substrates, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and the moon
The thickness of pole independently is 0.01 ~ 0.03mm.
Brief description of the drawings
Fig. 1 is the light emitting diode with quantum dots structural representation that the present invention makes.
Embodiment
The invention provides a kind of preparation method of light emitting diode with quantum dots, comprise the following steps：
（1）By including adulterate the molybdenum trioxide organic solution of a small amount of vanadium including the organic solution of triphenyl diamine polymer including
The organic solution of quantum dot and organic solution including zinc oxide are sequentially beaten by sol evenning machine spin coating method on conductive substrates surface
Print, obtains primary light emitting diode with quantum dots；
The molybdenum trioxide and organic solvent of a small amount of vanadium are adulterated in the molybdenum trioxide mixed organic solvents including adulterating a small amount of vanadium
Mass ratio be（8~15）:100；
The gross mass of triphenyl diamine polymer and organic solvent in the organic solution including triphenyl diamine polymer
Volume ratio is（5~10）mg：（1~2）mL；
The quality of quantum dot and the volume ratio of organic solvent are in the organic solution including quantum dot（5~25）mg：（1~2）
mL；
The quality of zinc oxide and the volume ratio of organic solvent are in the organic solution including zinc oxide（10~20）mg：（1~3）
mL；
（2）In the step（1）The superficial deposit electrode of obtained primary light emitting diode with quantum dots nonconductive matrix bottom side, is obtained
Light emitting diode with quantum dots.
The present invention by including adulterate a small amount of vanadium molybdenum trioxide organic solution including triphenyl diamine polymer it is organic molten
The organic solution of liquid including quantum dot and the organic solution including zinc oxide are by sol evenning machine spin coating method sequentially in conductive substrates
Printout surface, obtain primary light emitting diode with quantum dots.In the present invention, in the organic solution including vanadium and molybdenum trioxide
The mass ratio of the gross mass and organic solvent of vanadium and molybdenum trioxide is（8~15）:100, be preferably（12~14）:100, it is further excellent
Elect 13 as:100.In the present invention, organic solvent preferably includes ethanol, methanol, phenmethylol, second two in the mixed organic solvents
One kind or more in alcohol, n-butanol, isobutanol, neopentyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol and lauryl alcohol
Kind.In the present invention, the mol ratio of the vanadium and molybdenum trioxide is preferably（1~5）:（20~200）, more preferably（2~3）:（50~
150）, most preferably 2.5:100.For the present invention to the vanadium, the source of molybdenum trioxide and organic solvent does not have particular/special requirement, uses
Commercially available prod well-known to those skilled in the art.
In the present invention, the mixed organic solvents including vanadium and molybdenum trioxide preferably also include adjusting adhesive aggregation compound, institute
State and adjust the quality of adhesive aggregation compound to be preferably no greater than the 0.5% of vanadium and the molybdenum trioxide gross mass, more preferably 0.2 ~
0.3%.In the present invention, it is described to adjust adhesive aggregation compound to preferably include one in polyethylene, polypropylene, polyvinyl chloride and polystyrene
Kind is a variety of.The present invention does not have particular/special requirement to the source of the polyethylene, polypropylene, polyvinyl chloride and polystyrene, uses
Commercially available prod well-known to those skilled in the art.
In the present invention, it is described including triphenyl diamine polymer（poly-TPD）Organic solution in poly-TPD matter
Amount and the volume ratio of organic solvent are（5~10）mg：（1~2）ML, it is preferably（6~8）mg：（1~2）mL.In the present invention, it is described
Organic solvent is preferably included in chloro benzene,toluene,xylene, styrene, chloroform and benzene in organic solution including poly-TPD
One or more.The present invention does not have to the source of the poly-TPD, chloro benzene,toluene,xylene, styrene, chloroform and benzene
There is particular/special requirement, using commercially available prod well-known to those skilled in the art.
In the present invention, the organic solution including poly-TPD preferably also includes adjusting adhesive aggregation compound, the tune adhesive aggregation
The quality of compound is preferably no greater than the 0.5% of the poly-TPD mass, and more preferably 0.2 ~ 0.3%.In the present invention, institute
State and adjust adhesive aggregation compound consistent with the tune adhesive aggregation compound in above-mentioned technical proposal, will not be repeated here.
In the present invention, the quality of quantum dot and the volume ratio of organic solvent are in the organic solution including quantum dot
（5~25）mg：（1~2）ML, it is preferably（10~20）mg：1mL, more preferably（15~20）mg：1mL.In the present invention, institute
It is preferably II-IV compound semiconductors to state quantum dot, Group III-V compound semiconductor, group IV-VI compound semiconductor or I-
III-VI races semiconductor, more preferably ZnS, CdSe, HgTe, ZnSe, HgSe, CdS, ScNb and YNb one or more；
The form of the quantum dot is preferably nanocrystalline structure.The present invention does not have particular/special requirement to the specific source of the quantum dot, adopts
With well-known to those skilled in the art.
In the present invention, organic solvent preferably includes n-hexane, normal heptane, pungent in the organic solution including quantum dot
One or more in alkane, decane, hendecane, dodecane, n-tetradecane, hexadecane and n-octadecane.In the present invention, it is described
Organic solution including quantum dot preferably also includes tune adhesive aggregation compound, and the quality of the tune adhesive aggregation compound is preferably no greater than described
The 0.05% of poly-TPD mass, more preferably 0.02 ~ 0.03%.In the present invention, the tune adhesive aggregation compound and above-mentioned skill
Tune adhesive aggregation compound in art scheme is consistent, will not be repeated here.
In the present invention, the quality of zinc oxide and the volume ratio of solvent are in the organic solution including zinc oxide（10~
20）mg：（1~3）ML, it is preferably（12~18）mg：（1.5~2.5）ML, more preferably 15mg：2mL.In the present invention, the oxygen
It is preferably nano zine oxide to change zinc；The particle diameter of the zinc oxide is preferably
5 ~ 95nm, more preferably 10 ~ 60nm, more preferably 20nm.The present invention is not special to the source of the zinc oxide
It is required that using zinc oxide well-known to those skilled in the art.
In the present invention, organic solvent preferably includes ethanol, methanol, benzene first in the organic solution including zinc oxide
One in alcohol, ethylene glycol, n-butanol, isobutanol, neopentyl alcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol and lauryl alcohol
Kind is a variety of.The present invention to the ethanol, methanol, phenmethylol, ethylene glycol, n-butanol, isobutanol, neopentyl alcohol, hexanol, enanthol,
Octanol, nonyl alcohol, decyl alcohol, the source of undecyl alcohol and lauryl alcohol do not have particular/special requirement, using it is well-known to those skilled in the art i.e.
Can.In the present invention, the organic solution including zinc oxide preferably also includes adjusting adhesive aggregation compound, the matter for adjusting adhesive aggregation compound
The 0.5% of zinc oxide quality in the preferably no greater than described organic solution including zinc oxide of amount, more preferably 0.2 ~ 0.3%.
In the present invention, the tune adhesive aggregation compound is consistent with the tune adhesive aggregation compound in above-mentioned technical proposal, will not be repeated here.
The present invention by including adulterate the molybdenum trioxide organic solution of a small amount of vanadium including poly-TPD organic solution including
The organic solution of quantum dot and organic solution including zinc oxide are sequentially beaten by sol evenning machine spin coating method on conductive substrates surface
Print, obtains primary light emitting diode with quantum dots.
In the present invention, the conductive substrates preferably include one kind in metal oxide, metal simple-substance and carbonaceous material
It is or a variety of.In the present invention, the metal oxide preferably includes one in tin indium oxide, fluorine doped tin oxide and Al-Doped ZnO
Kind is a variety of；The metal simple-substance preferably includes metal nanometer line or wire netting (metal mesh), more preferably including silver nanoparticle
Line, nanowires of gold, copper nano-wire, the one or more in cupro-nickel wire netting, gold nano wire netting, copper nano metal net；Institute
State carbonaceous material and preferably include one or more in graphene, CNT and carbon nanocoils.
When the present invention prepares flexible quanta light emitting diode, the conductive substrates preferably use ITO electro-conductive glass.This
Invention does not have particular/special requirement to the specific source of the ITO electro-conductive glass, using commercially available production well-known to those skilled in the art
Product.
In the present invention, the cleaning treatment to the conductive substrates is preferably also included before the printing, removes conductive substrates
Upper dust, help the bonding of ink.The present invention does not have particular/special requirement to the cleaning treatment, ripe using those skilled in the art institute
The cleaning way for the substrate material surface known.
In the present invention, in the present invention, the molybdenum trioxide organic solution including adulterating a small amount of vanadium is revolved through sol evenning machine
Coating method obtains hole injection layer；The organic solution including poly-TPD obtains hole transport through sol evenning machine spin coating method
Layer；It is described to obtain quantum dot light emitting layer through sol evenning machine spin coating method including quantum dot organic solution；The having including zinc oxide
Machine solution obtains electron transfer layer through sol evenning machine spin coating method.
In the present invention, including the molybdenum trioxide organic solution of a small amount of vanadium of doping including triphenyl diamine polymer have
The volume ratio of the organic solution of machine solution including quantum dot and the organic solution including zinc oxide is preferably 1:1:1:1.
In the present invention, the sol evenning machine spin coating method.The present invention does not have to the embodiment of the sol evenning machine spin coating
There is particular/special requirement, using spin coating operation mode well-known to those skilled in the art.
In the present invention, the spin coating is preferably：Include the three of a small amount of vanadium of doping by described using sol evenning machine spin coating method
Molybdenum oxide organic solution obtains hole injection layer in conductive substrates surface spin coating；Using sol evenning machine spin coating method by the bag
The organic solution for including poly-TPD obtains hole transmission layer in hole injection layer surface spin coating；Using sol evenning machine spin coating method
The organic solution including quantum dot is obtained into quantum dot light emitting layer in the hole transport layer surface spin coating；Using sol evenning machine
The organic solution including zinc oxide is obtained electron transfer layer by spin coating method in the quantum dot light emitting layer surface spin coating.
In the present invention, the drying process to corresponding spin-coated layer is preferably also included after every layer of spin coating.In the present invention,
The time of drying after every layer of printing is preferably independently 30min, and the temperature of the drying after the spin coating every time is independently
Preferably 80 ~ 150 DEG C.In the present invention, the drying contributes to the volatilization of organic solvent, avoids organic solvent from sending out quantum dot
To the influence of luminous efficiency in photoreduction process.The present invention does not have particular/special requirement to the embodiment of the drying, using ability
Drying embodiment known to field technique personnel.
After obtaining the primary light emitting diode with quantum dots, the present invention is in the obtained primary light emitting diode with quantum dots
The superficial deposit electrode of nonconductive matrix bottom side, obtains light emitting diode with quantum dots.The present invention is preferably in the electron transfer layer table
Face evaporation cathode, obtains light emitting diode with quantum dots.In the present invention, the vacuum of the evaporation is preferably 1 × 10-6~9×
10-6Pa, more preferably 6 × 10-6~8×10-6Pa；In the present invention, the temperature of the evaporation is preferably 200 ~ 1200 DEG C,
More preferably 300 ~ 1000 DEG C, more preferably 400 ~ 500 DEG C.
In the present invention, the negative electrode preferably includes the one or more in aluminium, silver, copper and calcium；In the present invention, it is described
Negative electrode is more preferably yellow gold or aerdentalloy；When negative electrode uses the form of alloy, the present invention is in the alloy
The content of different component does not have particular/special requirement, using respective alloy well-known to those skilled in the art.
Present invention also offers the light emitting diode with quantum dots that the preparation method described in above-mentioned technical proposal obtains.In this hair
In bright, the light emitting diode with quantum dots, including set gradually conductive substrates, hole injection layer, hole transmission layer, quantum dot
Luminescent layer, electron transfer layer and negative electrode；The blended organic solution sol evenning machine spin coating of hole injection layer obtains；The hole passes
The defeated layer warp organic solution sol evenning machine spin coating including triphenyl diamine polymer obtains；Described in the quantum dot light emitting layer warp
Organic solution including quantum dot obtains through sol evenning machine spin coating；Include the organic solution of zinc oxide described in the electron transfer layer warp
Obtained through sol evenning machine spin coating.Light emitting diode with quantum dots structural representation is as shown in Figure 1
In the present invention, the conductive substrates, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and the moon
The thickness of pole is preferably independently 0.01 ~ 0.03mm, more preferably 0.02 ~ 0.025mm；In the present invention, the conduction
Substrate, hole injection layer, hole transmission layer, quantum dot light emitting layer, the thickness ratio of electron transfer layer and negative electrode are preferably 1:1:1:
1。
In order to further illustrate the present invention, with reference to embodiment to light emitting diode with quantum dots provided by the invention and its
Preparation method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
Poly-TPD and chlorobenzene are prepared in 6mg/ml ratios, obtain Poly-TPD organic solutions；Quantum dot normal octane is molten
Liquid is prepared in 15mg/ml ratios, obtains quantum dot solution；ZnO and ethanol are prepared in 10 mg/ml ratios, it is molten to obtain zinc oxide
Liquid；The molybdenum trioxide of a small amount of vanadium will be adulterated with ethanol by 11：100 ratios prepare, and obtain adulterating the molybdenum trioxide solution of a small amount of vanadium,
Wherein the mass ratio of vanadium and molybdenum trioxide is 3：100；
By molybdenum trioxide solution, Poly-TPD solution, quantum dot solution and the burnett's solution of a small amount of vanadium of doping of acquisition sequentially
Spin coating now on the glass substrate, is then toasted successively, and the volatilization of organic solvent is realized in baking process, obtains 0.01mm holes
Implanted layer, 0.01mm hole transmission layers, 0.01mm quantum dot light emitting layers and 0.01mm electron transfer layer primary quantum dot light emitting two
Pole pipe；Wherein, the spin coating of the molybdenum trioxide solution of a small amount of vanadium, Poly-TPD solution, quantum dot solution and burnett's solution is adulterated
It is 1 to measure volume ratio:1:1:1.
It is 9 × 10 in vacuum-6Pa, temperature are at 1000 DEG C, silver cathode are deposited in electric transmission layer surface, negative electrode is extremely thick
Spend for 0.01mm, obtain light emitting diode with quantum dots.
Embodiment 2
Poly-TPD and chlorobenzene are prepared in 6mg/ml ratios, obtain Poly-TPD ink；Quantum dot hexane solution is pressed
15mg/ml ratios prepare, and obtain quantum dot ink；ZnO ethanol solutions are prepared in 10 mg/ml ratios, obtain zinc oxid oil
Ink；The molybdenum trioxide of a small amount of vanadium will be adulterated with ethanol by 15：100 ratios prepare, and obtain adulterating the molybdenum trioxide solution of a small amount of vanadium,
Wherein the mass ratio of vanadium and molybdenum trioxide is 5：100；
By molybdenum trioxide solution, Poly-TPD solution, quantum dot solution and the burnett's solution of a small amount of vanadium of doping of acquisition sequentially
Spin coating now on the glass substrate, is then toasted successively, and the volatilization of organic solvent is realized in baking process, obtains 0.02mm holes
Implanted layer, 0.02mm hole transmission layers, 0.02mm quantum dot light emitting layers and 0.02mm electron transfer layer primary quantum dot light emitting two
Pole pipe；Wherein, the spin coating of the molybdenum trioxide solution of a small amount of vanadium, Poly-TPD solution, quantum dot solution and burnett's solution is adulterated
It is 1 to measure volume ratio:1:1:1.
It is 9 × 10 in vacuum-6Pa, temperature are at 1000 DEG C, zinc negative electrode are deposited in electric transmission layer surface, negative electrode is extremely thick
Spend for 0.01mm, obtain light emitting diode with quantum dots.
Embodiment 3
Poly-TPD and chlorobenzene are prepared in 6mg/ml ratios, according to the 0.02% of Poly-TPD mass, PVOH is added, obtains
To Poly-TPD ink；Quantum dot hexane solution is prepared in 5mg/ml ratios, it is poly- according to 0.02% addition of quantum point mass
Ethanol, obtain quantum dot ink；ZnO ethanol solutions are prepared in 20 mg/ml ratios, according to 0.02% addition of zinc oxide quality
PVOH, obtain zinc oxide ink；The molybdenum trioxide of a small amount of vanadium will be adulterated with ethanol by 13：100 ratios prepare, and it is few to obtain doping
The molybdenum trioxide solution of vanadium is measured, the wherein mass ratio of vanadium and molybdenum trioxide is 2.5：100；
By molybdenum trioxide solution, Poly-TPD solution, quantum dot solution and the burnett's solution of a small amount of vanadium of doping of acquisition sequentially
Spin coating now on the glass substrate, is then toasted successively, and the volatilization of organic solvent is realized in baking process, and it is thick empty to obtain 0.02mm
Cave implanted layer, 0.02mm hole transmission layers, 0.02mm quantum dot light emitting layers and 0.02mm electron transfer layer primary quantum dot light emittings
Diode；Wherein, the rotation of the molybdenum trioxide solution of a small amount of vanadium, Poly-TPD solution, quantum dot solution and burnett's solution is adulterated
Painting amount volume ratio is 1:1:1:1.
It is 9 × 10 in vacuum-6Pa, temperature are at 1000 DEG C, zinc negative electrode are deposited in electric transmission layer surface, negative electrode is extremely thick
Spend for 0.01mm, obtain light emitting diode with quantum dots.
Comparative example 1：
Solution is prepared according to the material rate of embodiment 1, the solution prepared is successively spin-coated onElectro-conductive glassOn conductive layer.
Spin coating process is in the argon inert atmosphere (O of glove box2<1ppm, H2O<1ppm) under carry out：
By molybdenum trioxide solution, with 2000r/s speed spin coating 40s on electro-conductive glass, then dried under the conditions of 150 DEG C
30min, obtain the hole injection layer that thickness is 0.01mm；
In hole injection layer surface spin coating Poly-TPD chloro benzole solns, according to 2000r/s speed spin coating 40s, vacuum is put into
20min is dried at 120 DEG C of drying box, obtains the hole transmission layer that thickness is 0.01mm；
In the normal octane solution of the CdSe quantum dot of hole transport layer surface spin coating, with 2500r/s speed spin coating 50s, 80
DEG C drying 10min, obtain thickness be 0.01mm quantum dot light emitting layer；
In quantum dot light emitting layer surface spin coating zinc oxide ethanol solution, with 2000r/s speed spin coating 40 seconds, then in 60 DEG C of bakings
Dry 30min, obtain the electron transfer layer that thickness is 0.01mm；
It is 9 × 10 in vacuum-6Pa, temperature are at 1000 DEG C, and silver cathode, negative electrode pole thickness is deposited in electric transmission layer surface
For 0.01mm, light emitting diode with quantum dots is obtained.
Comparative example 2：
Spin coating liquid is prepared according to the raw material of embodiment 2, the method according to comparative example 1 carries out spin coating and prepares quantum dot light-emitting diodes
Pipe.
Comparative example 3
Spin coating liquid is prepared according to the raw material of embodiment 3, the method according to comparative example 1 carries out spin coating and prepares quantum dot light-emitting diodes
Pipe.
The light emitting diode that the light emitting diode and comparative example 1 ~ 3 that embodiment 1 ~ 3 is prepared are prepared is sent out
The experimental test of luminous intensity, illuminance and colour gamut, test result are as shown in table 1.
The electroluminescent diode of preparation carries out luminous intensity, illuminance and colour gamut experiment, and test result is passed with using
Hard electroluminescent diode test result prepared by system method contrast as follows：
The test result table of comparisons for the light emitting diode that the embodiment 1 ~ 3 of table 1 and comparative example 1 ~ 3 are prepared
| Luminous intensity（cd） | Illuminance（lux） | Colour gamut | |
| Embodiment 1 | 165 | 52 | 110%NTSC CIE |
| Embodiment 2 | 167 | 50 | 110%NTSC CIE |
| Embodiment 3 | 169 | 49 | 110%NTSC CIE |
| Comparative example 1 | 165 | 47 | 110%NTSC CIE |
| Comparative example 2 | 157 | 46 | 110%NTSC CIE |
| Comparative example 3 | 155 | 47 | 110%NTSC CIE |
Compareed from the result of embodiment 1 and embodiment 2 in table 1, the concentration of quantum dot normal octane solution is higher, diode
Illumination effect is better；The control of the result of embodiment 1 and embodiment 3 understands that ZnO ethanol solution concentrations are higher, LED lighting effect
Fruit is better.
Described above is only the preferred embodiment of the present invention, not makees any formal limitation 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 preparation method of light emitting diode with quantum dots, comprises the following steps：
（1）By including adulterate the molybdenum trioxide organic solution of a small amount of vanadium including the organic solution of triphenyl diamine polymer including
The organic solution of quantum dot and the organic solution including zinc oxide by sol evenning machine spin coating method sequentially conductive substrates spin coating into
Film, obtain primary light emitting diode with quantum dots；
The mass ratio of the molybdenum trioxide and vanadium including adulterating the molybdenum trioxide solution of a small amount of vanadium is 1：（0.01~0.1）, solute
It is with organic solvent mass ratio（1~5）：100；
The quality of triphenyl diamine polymer and the body of organic solvent in the organic solution including triphenyl diamine polymer
Accumulating ratio is（5~10）mg：（1~2）mL；
The quality of quantum dot and the volume ratio of organic solvent are in the organic solution including quantum dot（5~25）mg：（1~2）
Ml；
The quality of zinc oxide and the volume ratio of organic solvent are in the organic solution including zinc oxide（10~20）mg：（1~3）
mL；
（2）In the step（1）The superficial deposit electrode of the bottom side at obtained primary light emitting diode with quantum dots nonconductive matrix bottom,
Obtain light emitting diode with quantum dots.
2. the preparation method of a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that the doping is few
Measuring organic solvent in the molybdenum trioxide organic solution of vanadium includes ethanol, methanol, phenmethylol, ethylene glycol, n-butanol, isobutanol, new
One or more in amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol and lauryl alcohol.
A kind of 3. preparation method of light emitting diode with quantum dots according to claim 1, it is characterised in that the triphenyl
In the organic solution of two amine polymers organic solvent include it is a kind of in chloro benzene,toluene,xylene, styrene, chloroform and benzene or
It is a variety of.
A kind of 4. preparation method of light emitting diode with quantum dots according to claim 1, it is characterised in that the quantum dot
Organic solution in organic solvent include n-hexane, normal heptane, octane, decane, hendecane, dodecane, n-tetradecane, hexadecane
With the one or more in n-octadecane.
A kind of 5. preparation method of light emitting diode with quantum dots according to claim 1, it is characterised in that the zinc oxide
Organic solution in organic solvent include ethanol, methanol, phenmethylol, ethylene glycol, n-butanol, isobutanol, neopentyl alcohol, hexanol, heptan
One or more in alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol and lauryl alcohol.
A kind of 6. preparation method of light emitting diode with quantum dots according to claim 1, it is characterised in that the step
（1）Include adulterating the molybdenum trioxide organic solution of a small amount of vanadium including the organic solution including quantum of triphenyl diamine polymer
The volume ratio of the organic solution of point and the organic solution including zinc oxide is 1:1:1:1.
A kind of 7. preparation method of light emitting diode with quantum dots according to any one of claim 1 ~ 6, it is characterised in that institute
State step（1）In each solution independently also include adjusting adhesive aggregation compound, the tune viscosity polymer includes polyethylene, polypropylene, poly-
One or more in vinyl chloride and polystyrene.
A kind of 8. preparation method of light emitting diode with quantum dots according to claim 7, it is characterised in that the step
（1）In adjust in each solution adhesive aggregation compound the Solute mass of low quality in corresponding solution 0.05%.
9. the light emitting diode with quantum dots that any one of claim 8 preparation method obtains, including the conductive base set gradually
Bottom, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and negative electrode；The hole injection layer is blended to be had
Machine solution obtains through sol evenning machine spin coating；The hole transmission layer warp organic solution including triphenyl diamine polymer is through even
Glue machine spin coating obtains；The quantum dot light emitting layer warp organic solution including quantum dot obtains through sol evenning machine spin coating；It is described
The electron transfer layer warp organic solution including zinc oxide obtains through sol evenning machine spin coating.
10. light emitting diode with quantum dots according to claim 9, it is characterised in that the conductive substrates, hole injection
Layer, hole transmission layer, quantum dot light emitting layer, the thickness of electron transfer layer and negative electrode independently are 0.01 ~ 0.03mm.
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| CN110400886A (en) * | 2018-04-24 | 2019-11-01 | 三星电子株式会社 | Luminescent film, its manufacturing method and luminescent device and display device containing the luminescent film |
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