CN108987597A - The composition of ambient stable storage and the preparation method of light emitting diode with quantum dots device - Google Patents
The composition of ambient stable storage and the preparation method of light emitting diode with quantum dots device Download PDFInfo
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- CN108987597A CN108987597A CN201810787832.0A CN201810787832A CN108987597A CN 108987597 A CN108987597 A CN 108987597A CN 201810787832 A CN201810787832 A CN 201810787832A CN 108987597 A CN108987597 A CN 108987597A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
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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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- H—ELECTRICITY
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- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
Abstract
The present invention discloses a kind of composition for capableing of ambient stable storage, including stable dispersions and flocculant, the stable dispersions include electron transfer layer nanoparticle, ligand and solvent, and the flocculant is used in mixed way with stable dispersions.Invention additionally discloses a kind of production methods of light emitting diode with quantum dots device, and wherein the making step of electron transfer layer includes: to provide the composition；The flocculant is made an addition in the stable dispersions, then the electron transfer layer is made annealing treatment in making electron transfer layer in first electrode using the mixture of formation later.Compared to the prior art, the storage that composition of the invention can be stable is at room temperature.In the manufacturing process of light emitting diode with quantum dots device, with the increase of annealing time, the ligand of electron transfer layer nanoparticle surface falls off, and the carrying cost in production process thus can also be reduced while guaranteeing light emitting diode with quantum dots element manufacturing effect.
Description
Technical field
The present invention relates to organic electroluminescence device technical fields, are specifically related to a kind of group for capableing of ambient stable storage
The production method for closing object and light emitting diode with quantum dots device.
Background technique
High with luminous efficiency based on the luminous light emitting diode with quantum dots device (QLEDs) of semiconductor-quantum-point (QDs),
The advantages that excitation purity is high and luminescent color is simply adjustable.In recent years, the exploitation of quanta point material and QLED device is received
More and more concerns.Compared with organic light emitting diode device, the luminescent layer in QLED device is by inorganic nano-particle subgroup
At.In the QLED manufacturing process of current mainstream, electron transfer layer is this using inorganic metal oxide nano-material
Nanoparticle is a kind of direct band gap broad stopband nanoparticle, electron mobility with higher.But electron transfer layer is usually
There is no the nanoparticle of ligand, because thering is the nanoparticle of ligand to be used in meeting in electron transfer layer so that electron-transport is obstructed,
Reduce QLED parameters.But the nano particle of ligand is not placed can cure at room temperature, so that nano-particles size becomes
Change, QLED device effect can be made to be deteriorated, the storage of usual electron transfer layer nanoparticle is to be stored using low temperature, but low temperature is deposited
Storage, it will increase enterprise's production cost.
Therefore, the storage cost of electron transfer layer how is reduced, and easily realizes volume production, production cost is reduced, becomes
Urgent problem to be solved.
Summary of the invention
The main purpose of the present invention is to provide a kind of two poles of composition and quantum dot light emitting for capableing of ambient stable storage
The production method of tube device, to overcome deficiency in the prior art.To realize aforementioned invention purpose, the technical side that the present invention uses
Case includes:
The embodiment of the invention provides a kind of compositions for capableing of ambient stable storage, including stable dispersions and flocculation
Agent；
The stable dispersions include electron transfer layer nanoparticle, ligand and solvent；
The flocculant is used in mixed way with stable dispersions.
The embodiment of the present invention also provides a kind of production method of light emitting diode with quantum dots device, including the first electricity of production
The step of pole, electron transfer layer, hole blocking layer, quantum dot light emitting layer, hole transmission layer, hole injection layer and second electrode,
The making step of the electron transfer layer includes:
Composition of any of claims 1-5 is provided；
The flocculant is made an addition in the stable dispersions, later using the mixture of formation in being made in first electrode
Make electron transfer layer, then the electron transfer layer is made annealing treatment.
Compared with prior art, the beneficial effect comprise that
(1) composition provided in an embodiment of the present invention for capableing of ambient stable storage, including stable dispersions and flocculant,
Stable dispersions include electron transfer layer nanoparticle, ligand and solvent, and flocculant is used in mixed way with stable dispersions, Ke Yishi
Store electron transfer layer nanoparticle at room temperature now.
(2) in the manufacturing process of light emitting diode with quantum dots device, with the increase of annealing time, electron transfer layer is received
The concentration of rice corpuscles is gradually increased, after reaching a certain concentration, due to the presence of flocculant, so that electron transfer layer nanoparticle sublist
The ligand in face falls off, then is cleaned by solvent to matrix, to remove ligand and flocculant therein.So that electronics passes
Defeated layer nanoparticle can be stable storage at room temperature, dropped while guaranteeing light emitting diode with quantum dots element manufacturing effect
Carrying cost in low production process.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the song that QLED device current efficiency and external quantum efficiency change with brightness change in the embodiment of the present invention one
Line chart；
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
One kind provided in an embodiment of the present invention is capable of the composition of ambient stable storage, including stable dispersions and flocculation
Agent；
The stable dispersions include electron transfer layer nanoparticle, ligand and solvent；
The flocculant is used in mixed way with stable dispersions.
Specifically, the surface of electron transfer layer nanoparticle can store at room temperature after ligand and flocculant is added.
In some embodiments, the ligand includes Sodium Polyacrylate, kayexalate, polyvinyl phosphates
Sodium, any one in polyacrylic acid potassium, polystyrolsulfon acid potassium and polyvinyl phosphates potassium or two or more combinations.
In some embodiments, the flocculant includes sodium chloride and/or potassium chloride.
In some embodiments, the size of the electron transfer layer nanoparticle is 3-5nm.
In some embodiments, in the mixed system formed after the flocculant is mixed with stable dispersions, flocculation
The concentration of agent is 10mmol/ml-30mmol/ml.
In some embodiments, the concentration of ligand is 30mmol/ml-50mmol/ml in the stable dispersions.
In some embodiments, the electron transfer layer nanoparticle includes ZnO, TiO2、SnO、ZrO2、Ta2O3、
Any one in ZnSnO and InSnO n-type semiconductor or two or more combinations.
In some embodiments, the electron transfer layer nanoparticle include doped with Mg, Li, Hg, Al, Ni, Mn,
The n-type semiconductor of any one or two or more elements in Co, Ga, In, Sb, Er, Sr, Cu, Y, Nd and Pd.
Electron transfer layer nanoparticle, which is selected, to be had compared with high electron mobility and the good n-type semiconductor of translucency.
The embodiment of the present invention also provides a kind of production method of light emitting diode with quantum dots device, including the first electricity of production
The step of pole, electron transfer layer, hole blocking layer, quantum dot light emitting layer, hole transmission layer, hole injection layer and second electrode,
The making step of the electron transfer layer includes:
The composition is provided；
The flocculant is made an addition in the stable dispersions, later using the mixture of formation in being made in first electrode
Make electron transfer layer, then the electron transfer layer is made annealing treatment.
In some embodiments, the annealing temperature of the annealing is 50-100 DEG C, time 10-100min.
In some embodiments, the material of the hole injection layer include PEDOT:PSS, CuPc, F4-TCNQ,
HATCN, molybdenum oxide, vanadium oxide, tungsten oxide, chromium oxide, in MoS2, WS2, MoSe2 and WSe2 any one or it is two or more
Combination.
In some embodiments, the material of the hole transmission layer include NPB, TPD, Poly-TPD, TFB, PVK,
Any one in CBP, TCTA and mCP or two or more combinations.
In some embodiments, the first electrode includes ITO electro-conductive glass.
In some specific embodiments, first ITO electro-conductive glass is cleaned: ITO electro-conductive glass piece is sequentially placed into
The beaker of acetone, alcohol and deionized water is filled, and is placed the beaker in ultrasonic washing instrument, is successively cleaned 10 minutes.It will wash
The ITO electro-conductive glass crossed is placed in a vacuum drying oven, and is dried for standby.
In some embodiments, the second electrode includes Al electrode or Ag electrode.
In some embodiments, the making step of the electron transfer layer is specifically included in depositing electronics in first electrode
Transport layer then makes annealing treatment the electron transfer layer, carries out cleaning later and removes the ligand and flocculant.
Specifically, after the annealing process, matrix being put into solvent and is cleaned, fall off to remove in electron transfer layer
Ligand and flocculant.
In some embodiments, the concentration of the electron transfer layer is 30mmol/ml-50mmol/ml, the stabilization point
The concentration of ligand is 30mmol/ml-50mmol/ml in dispersion liquid.
In some embodiments, the spin coating revolving speed is 1000r/min-5000r/min.
In some embodiments, the solvent selected by cleaning is any one or two in propylene glycol, glycerol and formic acid
Kind or more combination.
In some specific embodiments, a kind of production method of light emitting diode with quantum dots device may include following
Step:
(1) ITO electro-conductive glass cleans:
For example, ITO electro-conductive glass piece to be sequentially placed into the beaker for filling acetone, alcohol and deionized water, and beaker is set
In ultrasonic washing instrument, successively clean 10 minutes.Washed ITO electro-conductive glass is placed in a vacuum drying oven, is dried for standby；
(2) the depositing zinc oxide electron transfer layer on ITO electro-conductive glass, electron transfer layer can for ZnO, TiO2, SnO,
ZrO2, Ta2O3, AlZnO, ZnSnO and InSnO etc. have compared with the high electron mobility and good n-type semiconductor of translucency,
It anneals certain time under certain temperature, temperature range is between 50 DEG C -100 DEG C, and time range is between 10min-100min；Its
In, depositional mode can select spin coating or printing technology or other techniques；
(3) deposition of hole barrier layer on the electron transport layer；
(4) quantum dot light emitting layer is deposited on the hole blocking layer；
(5) the deposition of hole transport layer in quantum dot light emitting layer；Hole injection layer may include PEDOT:PSS, CuPc,
F4-TCNQ, HATCN, molybdenum oxide, vanadium oxide, tungsten oxide, chromium oxide, in MoS2, WS2, MoSe2 and WSe2 any one or
Two or more combinations；
(6) deposition of hole implanted layer on the hole transport layer；
(7) evaporation cathode on hole injection layer, cathode material can be metal Al or metal Ag.
The technical solution that present invention be described in more detail by the following examples.However, selected embodiment is only used for
Illustrate the present invention, and does not limit the scope of the invention.
Embodiment 1:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer ZnO of spin coating on ITO electro-conductive glass.
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of cathodic metal Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 10mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 70 DEG C,
Annealing time is 30min.Wherein, the concentration of ZnO is 30mmol/ml in electron transfer layer, and the concentration of ligand is 30mmol/ml,
The revolving speed of spin coating electron transfer layer is 1000r/min.
Referring to Figure 1, it can be seen that by the figure, make QLED device, QLED device using the electron transfer layer of the present embodiment
Current efficiency and external quantum efficiency are high, and device performance is excellent.
Embodiment 2:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer ZnO of spin coating on ITO electro-conductive glass.
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of cathodic metal Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 10mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 70 DEG C,
Annealing time is 30min.Wherein, the concentration of ZnO is 40mmol/ml in electron transfer layer, and the concentration of ligand is 40mmol/ml,
The revolving speed of spin coating electron transfer layer is 3000r/min.
Embodiment 3:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer TiO of spin coating on ITO electro-conductive glass2。
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of cathodic metal Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 10mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 50 DEG C,
Annealing time is 30min.Wherein, TiO in electron transfer layer2Concentration be 50mmol/ml, the concentration of the ligand is
50mmol/ml, the revolving speed of spin coating electron transfer layer are 5000r/min.
Embodiment 4:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer ZnO is printed on ITO electro-conductive glass.
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer is printed on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of cathodic metal Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 10mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporation, annealing temperature 100
DEG C, annealing time 10min.Wherein, the concentration of ZnO is 50mmol/ml in electron transfer layer, and the concentration of ligand is 50mmol/
ml。
Embodiment 5:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer SnO of spin coating on ITO electro-conductive glass.
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 20mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 80 DEG C,
Annealing time is 30min.Wherein, the concentration of SnO is 30mmol/ml in electron transfer layer, and the concentration of ligand is 30mmol/ml,
The revolving speed of spin coating electron transfer layer is 1000r/min.
Embodiment 6:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer ZnO of spin coating on ITO electro-conductive glass.
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 20mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 70 DEG C,
Annealing time is 70min.Wherein, the concentration of ZnO is 40mmol/ml in electron transfer layer, and the concentration of ligand is 40mmol/ml,
The revolving speed of spin coating electron transfer layer is 3000r/min.
Embodiment 7:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer ZrO of spin coating on ITO electro-conductive glass2。
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 20mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 90 DEG C,
Annealing time is 50min.Wherein, ZrO in electron transfer layer2Concentration be 50mmol/ml, the concentration of ligand is 50mmol/ml,
The revolving speed of spin coating electron transfer layer is 5000r/min.
Embodiment 8:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer Ta of spin coating on ITO electro-conductive glass2O3。
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 30mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 70 DEG C,
Annealing time is 30min.Wherein, Ta in electron transfer layer2O3Concentration be 30mmol/ml, the concentration of ligand is 30mmol/ml,
The revolving speed of spin coating electron transfer layer is 1000r/min.
Embodiment 9:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer ZnO of spin coating on ITO electro-conductive glass.
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 30mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 70 DEG C,
Annealing time is 30min.Wherein, the concentration of ZnO is 40mmol/ml in electron transfer layer, and the concentration of ligand is 40mmol/ml,
The revolving speed of spin coating electron transfer layer is 3000r/min.
Embodiment 10:
(1) ITO is cleaned: ito glass piece being sequentially placed into the beaker for filling acetone, alcohol and deionized water, and by beaker
It is placed in ultrasonic washing instrument, successively cleans 10 minutes.Washed ITO is placed in a vacuum drying oven, is dried for standby.
(2) one layer of electron transfer layer ZnO of spin coating on ITO electro-conductive glass.
(3) one layer of hole blocking layer of spin coating on the electron transport layer.
(4) one layer of quantum dot light emitting layer of spin coating on the hole blocking layer.
(5) one layer of hole transmission layer of spin coating on quantum dot light emitting layer.
(6) spin coating hole injection layer on the hole transport layer.
(7) on hole injection layer, one layer of Al electrode is deposited.
Above-mentioned steps (2) add ligand in electron transfer layer and flocculant, ligand are Sodium Polyacrylate, and flocculant is chlorine
Change sodium, the concentration of flocculant is 30mmol/ml.After annealing, above-mentioned matrix is put into propylene glycol solvent and is cleaned, removal electricity
The ligand and flocculant to fall off in sub- transport layer.It is annealed again after annealing so that cleaning solvent evaporates, annealing temperature is 60 DEG C,
Annealing time is 50min.Wherein, the concentration of ZnO is 50mmol/ml in electron transfer layer, and the concentration of ligand is 50mmol/ml,
The revolving speed of spin coating electron transfer layer is 5000r/min.
In addition, inventor also refers to the mode of above embodiments, with the other raw materials and item listed in this specification
Part etc. is tested, and the electron transfer layer and efficient light emitting diode with quantum dots device for being easy to store can equally be made
Part.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from concept of the invention, other modification and improvement can also be made, these are all
It belongs to the scope of protection of the present invention.
Claims (10)
1. the composition that one kind is capable of ambient stable storage, it is characterised in that: including stable dispersions and flocculant；
The stable dispersions include electron transfer layer nanoparticle, ligand and solvent；
The flocculant is used in mixed way with stable dispersions.
2. composition according to claim 1, it is characterised in that: the ligand includes Sodium Polyacrylate, polystyrene sulphur
Sour sodium, polyvinyl phosphates sodium, any one in polyacrylic acid potassium, polystyrolsulfon acid potassium and polyvinyl phosphates potassium
Or two or more combination；And/or the flocculant includes sodium chloride and/or potassium chloride.
3. composition according to claim 1, it is characterised in that: the size of the electron transfer layer nanoparticle is 3-
5nm。
4. composition according to claim 1, it is characterised in that: formed after the flocculant is mixed with stable dispersions
Mixed system in, the concentration of flocculant is 10mmol/ml-30mmol/ml；And/or in the stable dispersions ligand it is dense
Degree is 30mmol/ml-50mmol/ml.
5. composition according to claim 1, it is characterised in that: the electron transfer layer nanoparticle includes ZnO, TiO2、
SnO、ZrO2、Ta2O3, any one or two or more combinations in ZnSnO and InSnO n-type semiconductor；And/or institute
Stating electron transfer layer nanoparticle includes doped with Mg, Li, Hg, Al, Ni, Mn, Co, Ga, In, Sb, Er, Sr, Cu, Y, Nd and Pd
In any one or two or more elements n-type semiconductor.
6. a kind of production method of light emitting diode with quantum dots device, including production first electrode, electron transfer layer, hole barrier
The step of layer, quantum dot light emitting layer, hole transmission layer, hole injection layer and second electrode, which is characterized in that the electron-transport
Layer making step include:
Composition of any of claims 1-5 is provided；
The flocculant is made an addition in the stable dispersions, it is electric in being made in first electrode using the mixture formed later
Sub- transport layer then makes annealing treatment the electron transfer layer.
7. production method according to claim 6, which is characterized in that the annealing temperature of the annealing is 50-100
DEG C, time 10-100min.
8. production method according to claim 6, it is characterised in that: the material of the hole injection layer includes PEDOT:
PSS, CuPc, F4-TCNQ, HATCN, molybdenum oxide, vanadium oxide, tungsten oxide, chromium oxide, appointing in MoS2, WS2, MoSe2 and WSe2
Meaning a combination of one or more；And/or the material of the hole transmission layer include NPB, TPD, Poly-TPD, TFB,
Any one in PVK, CBP, TCTA and mCP or two or more combinations；And/or the first electrode includes ITO conduction glass
Glass；And/or the second electrode includes Al electrode or Ag electrode.
9. production method according to claim 6, it is characterised in that: the making step of the electron transfer layer specifically includes
In depositing electron transfer layer in first electrode, then the electron transfer layer is made annealing treatment, carries out cleaning removal later
The ligand and flocculant.
10. manufacturing method according to claim 9, it is characterised in that: the concentration of the electron transfer layer is 30mmol/
Ml-50mmol/ml, the concentration of ligand is 30mmol/ml-50mmol/ml in the stable dispersions；And/or the spin coating turns
Speed is 1000r/min-5000r/min；And/or cleaning selected solvent is any one in propylene glycol, glycerol and formic acid
Or two or more combination.
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| WO2023197659A1 (en) * | 2022-04-14 | 2023-10-19 | Tcl科技集团股份有限公司 | Manufacturing method for light emitting device, light emitting device, and display apparatus |
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