CN109935705A - Hole-injecting material and preparation method thereof and QLED device - Google Patents
Hole-injecting material and preparation method thereof and QLED device Download PDFInfo
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Abstract
The invention belongs to technology of quantum dots fields more particularly to a kind of hole-injecting material and preparation method thereof and QLED device.The hole-injecting material includes p-type ZnO, and the p-type ZnO is phosphorus doping ZnO nano material, and the p-type ZnO surface modification has fatty acid.The hole-injecting material improves the acceptor level of p-type ZnO nano material, reduce the forbidden bandwidth of ZnO, inhibit self-compensation mechanism, to improve the injectability in hole, promote electron-hole effectively compound, influence of the exciton accumulation to device performance is reduced, to improve the luminescent properties of QLED device.
Description
Technical field
The invention belongs to quantum dot fields, and in particular to a kind of hole-injecting material and preparation method thereof and QLED device.
Background technique
ZnO is a kind of n-type semiconductor of direct band gap, the low work content of broad stopband and 3.7eV with 3.37eV, this
Kind band structure feature determines that ZnO can become suitable electron transport layer materials；Its good electric conductivity, high visible simultaneously
The preparation process of transmitance, excellent water oxygen stability and maturation has it increasingly in the photoelectric device of solution process
Outstanding performance.
ZnO depends on the N-shaped of high quality and the preparation of p-type thin film in the application of photoelectric field.People pass through doping at present
Oneself is through obtaining the N-shaped ZnO with preferable electric property.However intrinsic ZnO is easy to produce various donor-type defects in inside, hair
Being born from compensating action makes p-type ZnO film be difficult to prepare, and such case largely limits ZnO film in photoelectric device
The development of aspect, therefore the p-type ZnO film for how being doped acquisition high quality is always the difficult point and heat of ZnO research field
Point.Therefore, the existing technology needs to be improved and developed.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of hole-injecting material and its preparation side are provided
Method and QLED device, it is intended to solve the technical issues of prior art can not form the p-type ZnO of high quality.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of hole-injecting material, including p-type ZnO, the p-type ZnO are phosphorus doping ZnO nano
Material, and the p-type ZnO surface modification has fatty acid.
Correspondingly, a kind of preparation method of hole-injecting material, includes the following steps:
Zinc salt and phosphate are provided；
The zinc salt and phosphate are dissolved in organic solvent, the first heat treatment is carried out under the first alkaline condition, is obtained
Phosphorus doping zincite crystal solution；
Fatty acid is provided, the fatty acid is added in the phosphorus doping zincite crystal solution, in the second alkaline condition
Precursor solution is heated to obtain in lower progress second；
The precursor solution is placed on substrate, carries out making annealing treatment to obtain the hole-injecting material.
Another aspect of the present invention provides a kind of QLED device, including hole injection layer, and the hole injection layer is the present invention
Above-mentioned hole-injecting material.
Correspondingly, a kind of preparation method of QLED device, the QLED device, which is positive, sets type QLED device, and the QLED
Device includes hole injection layer, and the preparation method includes the following steps:
Substrate is provided, is provided with anode on the substrate；
Hole-injecting material, shape are prepared on the anode using the preparation method of above-mentioned hole-injecting material of the invention
At the hole injection layer.
Alternatively, a kind of preparation method of QLED device, the QLED device is to invert type QLED device, and the QLED device
Part includes hole injection layer, and the preparation method includes the following steps:
Substrate is provided, is provided with quantum dot light emitting layer on the substrate；
Hole note is prepared on the quantum dot light emitting layer using the preparation method of above-mentioned hole-injecting material of the invention
Enter material, forms the hole injection layer.
Hole-injecting material provided by the invention is a kind of phosphorus doping ZnO nano material: phosphorus substitutes oxygen atom lattice position.
Since the donor-type defect of ZnO is more readily formed than acceptor type defect, the presence of these Shi zhimings can compensate for acceptor-type defect
And lead to self-compensation mechanism, however group Ⅴ element phosphorus replaces the oxygen atom in ZnO, can receive an electronics from valence band, improves
Acceptor level forms the effective p-type doping of ZnO.And when adulterating phosphorus, related with phosphorus Shi zhiming exists, can be with
The acceptor-type defect of ZnO is compensated, this restrained effectively self-compensation mechanism.After predicting phosphorus doping according to density functional theory (DFT)
The Po acceptor level of formation is 1.13eV, and the raising of acceptor level can reduce the forbidden bandwidth of ZnO from intrinsic 3.4eV to P-
The 2.2eV of ZnO increases the injection efficiency in hole, promotes electron-hole effectively compound, reduces exciton accumulation to device performance
Influence.Carboxylic acid ion in fatty acid has a polyelectron pi bond, after the electronics that the offer of a metal Zn atom is provided,
It is formed and is conjugated with carboxyl, can closely cooperated on the surface ZnO；Fatty acid other end is that the organic matter of alkyl chain is repaired
Decorations, improve dissolubility and dispersibility of the ZnO in polarity or nonpolar solvent.
The preparation method of hole-injecting material of the invention is prepared for a kind of fatty acid by simple sol-gel method
The phosphorus doping ZnO nano material (P-ZnO) of modification is used as hole injection layer material.The preparation method is by improving p-type ZnO nano
The acceptor level of material reduces the forbidden bandwidth of ZnO, it is suppressed that self-compensation mechanism etc. is adjusted, to improve the note in hole
Enter ability, promote electron-hole effectively compound, influence of the exciton accumulation to device performance is reduced, to improve QLED device
Luminescent properties.The present invention can both dissolve polar solvent by the P doping zinc oxide nanometer material (P-ZnO) of fatty acid modifying,
Nonpolar dissolution can be dissolved, versatility is stronger, preparation method very simple, is suitble to large area, large scale preparation.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the QLED device in the embodiment of the present invention 4.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
On the one hand, the embodiment of the present invention provides a kind of hole-injecting material, including p-type ZnO, the p-type ZnO are phosphorus doping
ZnO nano material, and the p-type ZnO surface modification has fatty acid.
Hole-injecting material provided in an embodiment of the present invention is a kind of phosphorus doping ZnO nano material: it is brilliant that phosphorus substitutes oxygen atom
Case.Since the donor-type defect of ZnO is more readily formed than acceptor type defect, the presence of these Shi zhimings can compensate for acceptor
Defect and lead to self-compensation mechanism, however group Ⅴ element phosphorus replace ZnO in oxygen atom, can from valence band receive an electronics,
Acceptor level is improved, the effective p-type doping of ZnO is formed.And when adulterating phosphorus, Shi zhiming related with phosphorus exists,
The acceptor-type defect of ZnO can be compensated, this restrained effectively self-compensation mechanism.Predict that phosphorus is mixed according to density functional theory (DFT)
The Po acceptor level formed after miscellaneous is 1.13eV, and the raising of acceptor level can reduce the forbidden bandwidth of ZnO from intrinsic 3.4eV
To the 2.2eV of P-ZnO, increase the injection efficiency in hole, promote electron-hole effectively compound, reduces exciton accumulation to device
The influence of performance.Carboxylic acid ion in fatty acid has a polyelectron pi bond, receives the electronics of metal Zn atom offer
Afterwards, it is formed and is conjugated with carboxyl, can closely cooperated on the surface ZnO；Fatty acid other end is that the organic matter of alkyl chain carries out
Modification, improves dissolubility and dispersibility of the ZnO in polarity or nonpolar solvent.
Correspondingly, a kind of preparation method of hole-injecting material, includes the following steps:
S01: zinc salt and phosphate are provided；
S02: the zinc salt and phosphate are dissolved in organic solvent, are carried out at the first heating under the first alkaline condition
Reason, obtains phosphorus doping zincite crystal solution；
S03: providing fatty acid, and the fatty acid is added in the phosphorus doping zincite crystal solution, in the second alkalinity
Under the conditions of carry out second heating to obtain precursor solution；
S04: the precursor solution is placed on substrate, carries out making annealing treatment to obtain the hole-injecting material.
The preparation method of the hole-injecting material of the embodiment of the present invention is prepared for one kind by simple sol-gel method
The phosphorus doping ZnO nano material (P-ZnO) of fatty acid modifying is used as hole injection layer material.The preparation method is by improving p-type
The acceptor level of ZnO nano material reduces the forbidden bandwidth of ZnO, it is suppressed that self-compensation mechanism etc. is adjusted, to improve sky
The injectability in cave promotes electron-hole effectively compound, influence of the exciton accumulation to device performance is reduced, to improve
The luminescent properties of QLED device.The present invention can both dissolve pole by the P doping zinc oxide nanometer material (P-ZnO) of fatty acid modifying
Property solvent, nonpolar dissolution can also be dissolved, versatility is stronger, preparation method very simple, is suitble to large area, extensive system
It is standby.
Further, in above-mentioned steps S02, mole of the phosphonium ion in zinc ion and the phosphate in the zinc salt
Than for 1:(0.001-0.1).Specifically, in phosphorus doping zincite crystal solution the molar ratio of zinc ion and phosphonium ion to subsequent system
Standby hole-injecting material performance is affected, it is preferable that the molar ratio of zinc ion and phosphonium ion is controlled in 1:(0.001-
0.1).After phosphorus doping amount reaches certain value (being greater than 10%), solid solubility of the phosphorus in ZnO reaches saturation, and doping continues to increase
When big, phosphorus can be gathered in the surface of ZnO crystal grain, form cenotype, reduce the effective ratio area of nano-ZnO；Phosphorus enters ZnO's
Intracell causes the expansion of lattice, generates biggish distortion of lattice and strain energy, i.e. the increase of doping can cause lattice
Mutation, forms new lattice and Zn3P2Generation.When phosphorus doping amount is too low, then phosphorus is lost during the reaction, can not
Realize effective doping.
Further, in above-mentioned steps S03, the molar ratio of the zinc ion in the fatty acid and the zinc salt is (2-3):
1.When the molar ratio of fatty acid and zinc salt is (2-3): when 1, the partial size of prepared Zinc oxide nanoparticle is minimum.According to theory
It calculates, is just reacted when fatty acid and the molar ratio of zinc salt are 1:1, but when molar ratio is 1:1, partial size is bigger, and reason exists
In when mole smaller, with the progress that raw material reacts, the concentration of fatty acid is smaller and smaller, reacts the very slow of change, and cannot
It is adsorbed on nano grain surface completely；When molar ratio is excessive, on the one hand reaction is carried out too fast, on the other hand, is moved back in high temperature
When fiery, excess fat acid is not easy to remove, and might have remnants.
Fatty acid is a kind of common organic modifier due to high chemical stability and high balance binding constants.Rouge
Carboxylic acid ion in fat acid has a polyelectron pi bond, after the electronics for receiving the offer of a metal Zn atom, is formed with carboxyl
Conjugation, can closely cooperate on the surface ZnO；Other end is that the organic matter of alkyl chain is modified, improve ZnO in polarity or
Dissolubility and dispersibility in nonpolar solvent.The fatty acid can be selected from saturated fatty acid or unsaturated fatty acid, example
Such as: saturated fatty acid can be selected from stearic acid, palmitic acid, lauric acid, enanthic acid, octanoic acid or capric acid but not limited to this；Unsaturated fat
Acid is linoleic acid, linolenic acid or arachidonic acid but not limited to this.
Further, in the preparation method of above-mentioned hole-injecting material, the pH of first alkaline condition is 12-13；Institute
The pH for stating the second alkaline condition is 8-9.First alkaline condition and the second alkaline condition can pass through lye (such as organic base and/or nothing
Machine alkali) pH is adjusted, specifically, in the first alkaline condition, lye hydroxide ion mole and zinc ion can be passed through
Mole ratio be (1.8-2.5): 1 is adjusted, when the sum of the mole of hydroxide ion and zinc ion ratio be less than 1.8:1,
Metal salt is excessive, and cannot being doped completely for phosphorus is added；When greater than 2.5:1, pH value is excessively high to will lead to polycondensation speed in system
It will slow down.Optimally, keeping the molar ratio ratio of hydroxide ion and zinc ion is (1.8-2.5):, it can be achieved that the first alkali when 1
The pH12-13 of property condition, may finally make the subsequent P-ZnO film for obtaining consolidation densification, film surface even particle distribution.
According to colloid-stabilised dlvo theory, the Zeta potential of colloid is bigger, and the stability of colloid is better.Zinc oxide precursor
Body micelle is positively charged, and Zeta potential is positive, as pH value increases, OH-Concentration increases, so that Zeta potential reduces, between micelle
It is easy to assemble and becomes larger particles, causes to be easy to happen sedimentation.Therefore, fast when pH value is more than 10 under the second alkaline condition
Speed generates precipitating, and no colloid generates, if but pH value it is too low, acidity is too big, also is not easy to form colloid.Optimally, the second alkaline item
The pH of part is controlled in 8-9.
Further, in the preparation method of above-mentioned hole-injecting material, first alkaline condition and second alkalinity
The pH of condition is provided by lye, and the lye is selected from ammonium hydroxide, potassium hydroxide solution, sodium hydroxide solution, ethanolamine solutions, second two
At least one of alcoholic solution, diethanolamine solution, triethanolamine solution and ethylenediamine solution.The zinc salt be selected from zinc acetate,
At least one of zinc nitrate, zinc chloride, zinc sulfate and acetic acid dihydrate zinc；Phosphate is selected from dihydric phosphate, one hydrogen of phosphoric acid
At least one of salt and phosphoric acid normal salt；Fatty acid is selected from saturated fatty acid and/or non-saturated fatty acid；Organic solvent is selected from second
At least one of glycol methyl ether, propylene glycol monomethyl ether, isopropanol, ethyl alcohol, propyl alcohol, butanol and acetone.
The embodiment of the present invention also provides a kind of QLED device, including hole injection layer, and the hole injection layer is by the present invention
The above-mentioned hole-injecting material of embodiment forms.
Correspondingly, a kind of preparation method of QLED device, the QLED device, which is positive, sets type QLED device, and the QLED
Device includes hole injection layer, and the preparation method includes the following steps:
Substrate is provided, is provided with anode on the substrate；
Hole is prepared on the anode using the preparation method of the above-mentioned hole-injecting material of the embodiment of the present invention to inject
Material forms the hole injection layer.
Alternatively, a kind of preparation method of QLED device, the QLED device is to invert type QLED device, and the QLED device
Part includes hole injection layer, and the preparation method includes the following steps:
Substrate is provided, is provided with quantum dot light emitting layer on the substrate；
It is prepared on the quantum dot light emitting layer using the preparation method of the above-mentioned hole-injecting material of the embodiment of the present invention
Hole-injecting material forms the hole injection layer.
It is so-called just to set type QLED device, that is, refer to adjacent with substrate in anode, other function is then stacked on anode
Layer.It is so-called to invert type QLED device, that is, refer to it is adjacent with substrate in cathode pole, then cathode extremely on be stacked other function
Layer.
In a specific embodiment, a kind of preparation method of QLED device includes the following steps:
A: a hole injection layer is grown first on substrate；Wherein the material of the hole injection layer is rouge as described above
The P doping zinc oxide nanometer material (P-ZnO) of fat acid modification.
B: and then the deposition of hole transport layer on hole injection layer；
C: quantum dot light emitting layer is then deposited on hole transmission layer；
D: electron transfer layer is finally deposited on quantum dot light emitting layer, and evaporation cathode is sent out on electron transfer layer
Optical diode.
The phosphorus doping ZnO nano material layer of the fatty acid modifying of high quality in order to obtain, ITO substrate are needed by pretreatment
Process.Basic specific processing step includes: to clean full wafer ITO electro-conductive glass with detergent, preliminary to remove existing for surface
Spot is then successively cleaned by ultrasonic 20min in deionized water, acetone, dehydrated alcohol, deionized water respectively, to remove surface
Existing impurity, is finally dried up with high pure nitrogen, and ITO anode can be obtained.
Further, the hole injection layer is the P doping zinc oxide nanometer material (P-ZnO) of fatty acid modifying.Hole injection
The preparation of layer includes: the solution spin-coating film with prepared hole injection layer material；By the concentration, the spin coating speed that adjust solution
Degree and spin-coating time control film thickness, then at 300 DEG C -350 DEG C thermal anneal process, hole injection layer with a thickness of 20-
60nm。
Further, the hole mobile material that this field routine can be used in the hole transmission layer is made, including but unlimited
In TFB, PVK, PEDOT:PSS, Poly-TPD, TCTA, CBP etc. or it is the mixture of any combination thereof, can also is other
High performance hole mobile material.Hole transmission layer: it after the substrate cooling of metal oxide hole injection layer in spin coating, sets
In on sol evenning machine, with the solution spin-coating film of prepared hole mobile material；By adjust the concentration of solution, spin speed and
Spin-coating time controls film thickness, then thermal anneal process at moderate temperatures, water-soluble hole injection layer with a thickness of 20-
60nm。
Further, the quantum dot of the quantum dot light emitting layer is one of three kinds of red, green, blue quantum dots.Can be
CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、
AlAs, AlP, CuInS, CuInSe and at least one of various nuclear shell structure quantum points or alloy structure quantum dot.It can be with
It can be with the step quantum dot can be for containing cadmium for three kinds of red, green, blue common any one quantum dot or other yellow lights
Or be free of cadmium.The quantum dot light emitting layer of the material has exciting light spectrum width and continuously distributed, emission spectrum stability height etc.
Feature.The preparation of luminescent layer: by the substrate sol evenning machine of hole transmission layer in spin coating, certain density shiner will be prepared
Matter solution spin-coating film controls the thickness of luminescent layer, about 20- by adjusting concentration, spin speed and the spin-coating time of solution
60nm is dried at moderate temperatures.
Further, the electron transport material that this field routine can be used in the electron transfer layer is made, including but unlimited
In for ZnO, TiO2、CsF、LiF、CsCO3And Alq3One of.The preparation of electron transfer layer: by luminescent layer in spin coating
Substrate is placed in vacuum evaporation chamber, and the electron transfer layer of one layer of about 80nm thickness is deposited, and evaporation rate is about 0.01-0.5nm/s,
It anneals at moderate temperatures.
Then, the substrate for having deposited each functional layer is placed in vapor deposition storehouse through one layer of 15-30nm's of mask plate hot evaporation
Perhaps aluminium as cathode or uses nanometer Ag line or Cu line to metallic silver, and there is lesser resistance to enable carrier smooth
Injection.
Further, obtained QLED being packaged processing, common machine encapsulation can be used in the encapsulation process,
It can be using encapsulation manually.Preferably, in the environment of the encapsulation process, oxygen content and water content are below 0.1ppm, to protect
Demonstrate,prove the stability of device.
The present invention successively carried out test of many times, and it is further detailed as reference pair invention progress now to lift A partial experiment result
Thin description, is described in detail combined with specific embodiments below.
Embodiment 1
For using zinc chloride, sodium dihydrogen phosphate, methanol, sodium hydroxide, oleic acid, the hole of the present embodiment is discussed in detail
The preparation method of injection material.
1) suitable zinc chloride and sodium dihydrogen phosphate being added in 50ml methanol and forming total concentration is the molten of 0.2M-1M
Liquid；Wherein, zinc: the molar ratio of phosphorus is 1:(0.1%-10%).Then the stirring and dissolving at 60 DEG C, it is molten to be added dropwise sodium hydroxide
Solution is in the lye of 10ml methanol；Wherein, sodium hydroxide: Zn2+Molar ratio=(1.8-2.5): 1.Continuation stirs 2h- at 60 DEG C
4h obtains a kind of uniform clear solution.
2) the 10ml methanol solution of oleic acid is slowly added dropwise；Wherein, oleic acid: Zn2+Molar ratio=(2-3): 1, pH=8-9,
Continue to form precursor solution in 60 DEG C of isothermal holding 1h-2h.
3) after precursor solution is cooling, with sol evenning machine spin coating on processed ITO, and in 300 DEG C of -350 DEG C of annealing.
Embodiment 2
By taking zinc nitrate, ammonium orthophosphate, ethylene glycol monomethyl ether, ammonium hydroxide, lauric acid as an example, the hole note of the present embodiment is discussed in detail
Enter the preparation method of material.
1) suitable zinc nitrate and ammonium orthophosphate being added in 50ml ethylene glycol monomethyl ether and forming total concentration is 0.2M-1M's
Solution；Wherein, zinc: the molar ratio of phosphorus is 1:(0.1%-10%).Then the stirring and dissolving at 60 DEG C, is added dropwise ammonia solvent
In the lye of 10ml ethylene glycol monomethyl ether；Wherein, ammonium hydroxide: Zn2+Molar ratio=(1.8-2.5): 1.Continuation stirs 2h- at 60 DEG C
4h obtains a kind of uniform clear solution.
2) lauric 10ml ethylene glycol monomethyl ether solution is slowly added dropwise；Wherein, lauric acid: Zn2+Mole :=(2-3): 1,
PH=8-9 continues to form precursor solution in 60 DEG C of isothermal holding 1h-2h.
3) spin coating and in 300 DEG C of -350 DEG C of annealing on processed ITO with sol evenning machine after precursor solution is cooling.
Embodiment 3
For using zinc sulfate, potassium hydrogen phosphate, ethyl alcohol, potassium hydroxide, stearic acid, the hole of the present embodiment is discussed in detail
The preparation method of injection material.
1) suitable zinc sulfate and potassium hydrogen phosphate are added to and form the solution that total concentration is 0.2M-1M in 50ml ethyl alcohol；
Wherein, zinc: the molar ratio of phosphorus is 1:(0.1%-10%).Then potassium hydroxide dissolution is added dropwise in the stirring and dissolving at 60 DEG C
In the lye of 10ml ethyl alcohol；Wherein, potassium hydroxide: Zn2+Molar ratio=(1.8-2.5): 1.Continuation stirs 2h-4h at 60 DEG C
Obtain a kind of uniform clear solution.
2) stearic 10ml ethanol solution is slowly added dropwise；Wherein, stearic acid: Zn2+Molar ratio=(2-3): 1, pH=
8-9 continues to form precursor solution in 60 DEG C of isothermal holding 1h-2h.
3) spin coating and in 300 DEG C of -350 DEG C of annealing on processed ITO with sol evenning machine after precursor solution is cooling.
Embodiment 4
A kind of QLED device, structure is as shown in Figure 1, the preparation method of the QLED device includes the following steps:
A: a hole injection layer is grown first on substrate；Wherein the material of the hole injection layer is to implement as described above
The phosphorus doping ZnO nano material (P-ZnO) of fatty acid modifying in example 1-3.
B: and then the deposition of hole transport layer on hole injection layer；
C: quantum dot light emitting layer is then deposited on hole transmission layer；
D: electron transfer layer is finally deposited on quantum dot light emitting layer, and evaporation cathode pole is obtained on electron transfer layer
Light emitting diode.
The QLED device of the present embodiment be eurymeric configuration, as shown in Figure 1, QLED device from below to up successively include substrate 1,
Anode 2, hole injection layer 3, hole transmission layer 4, quantum dot light emitting layer 5, electron transfer layer 6, cathode 7.Wherein, the material of substrate 1
Material is sheet glass, and the material of anode 2 is ito substrate, and the material of hole injection layer 3 is P-ZnO, and the material of hole transmission layer 4 is
TFB, the material of electron transfer layer 6 is ZnO and the material of cathode 7 is Al.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of hole-injecting material, which is characterized in that including p-type ZnO, the p-type ZnO is phosphorus doping ZnO nano material, and
The p-type ZnO surface modification has fatty acid.
2. a kind of preparation method of hole-injecting material, which comprises the steps of:
Zinc salt and phosphate are provided；
The zinc salt and phosphate are dissolved in organic solvent, the first heat treatment is carried out under the first alkaline condition, phosphorus is obtained and mixes
Miscellaneous zincite crystal solution；
Fatty acid is provided, the fatty acid is added in the phosphorus doping zincite crystal solution, under the second alkaline condition into
Row second heats to obtain precursor solution；
The precursor solution is placed on substrate, carries out making annealing treatment to obtain the hole-injecting material.
3. the preparation method of hole-injecting material as claimed in claim 2, which is characterized in that zinc ion in the zinc salt with
The molar ratio of phosphonium ion in the phosphate is 1:(0.001-0.1).
4. the preparation method of hole-injecting material as claimed in claim 2, which is characterized in that the fatty acid and the zinc salt
In zinc ion molar ratio be (2-3): 1.
5. the preparation method of hole-injecting material as claimed in claim 2, which is characterized in that the pH of first alkaline condition
For 12-13；And/or
The pH of second alkaline condition is 8-9.
6. the preparation method of hole-injecting material as claimed in claim 2, which is characterized in that first alkaline condition and institute
The pH for stating the second alkaline condition is provided by lye, and the lye is selected from ammonium hydroxide, potassium hydroxide solution, sodium hydroxide solution, ethyl alcohol
At least one of amine aqueous solution, ethylene glycol solution, diethanolamine solution, triethanolamine solution and ethylenediamine solution.
7. such as the preparation method of the described in any item hole-injecting materials of claim 2-5, which is characterized in that the zinc salt is selected from
At least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and acetic acid dihydrate zinc；And/or
The phosphate is selected from least one of dihydric phosphate, dibasic alkaliine and phosphoric acid normal salt；And/or
The fatty acid is selected from saturated fatty acid and/or non-saturated fatty acid；And/or
The organic solvent in ethylene glycol monomethyl ether, propylene glycol monomethyl ether, isopropanol, ethyl alcohol, propyl alcohol, butanol and acetone at least
It is a kind of.
8. a kind of QLED device, including hole injection layer, which is characterized in that the hole injection layer is sky described in benefit requires 1
Hole injection material.
9. a kind of preparation method of QLED device, the QLED device, which is positive, sets type QLED device, and the QLED device includes
Hole injection layer, which is characterized in that the preparation method includes the following steps:
Substrate is provided, is provided with anode on the substrate；
Hole-injecting material is prepared on the anode using the described in any item preparation methods of claim 2-7, described in formation
Hole injection layer.
10. a kind of preparation method of QLED device, the QLED device is to invert type QLED device, and the QLED device includes
Hole injection layer, which is characterized in that the preparation method includes the following steps:
Substrate is provided, is provided with quantum dot light emitting layer on the substrate；
Hole-injecting material is prepared on the quantum dot light emitting layer using the described in any item preparation methods of claim 2-7,
Form the hole injection layer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020031680A1 (en) * | 1998-08-03 | 2002-03-14 | White Henry W. | Zinc oxide films containing p-type dopant and process for preparing same |
| CN101125677A (en) * | 2007-09-16 | 2008-02-20 | 中国日用化学工业研究院 | Method for preparing high dispersity nano zinc oxide |
| CN101960603A (en) * | 2008-01-08 | 2011-01-26 | 莫克斯特尼克公司 | High-performance heterostructure light emitting devices and methods |
-
2017
- 2017-12-15 CN CN201711349350.9A patent/CN109935705B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020031680A1 (en) * | 1998-08-03 | 2002-03-14 | White Henry W. | Zinc oxide films containing p-type dopant and process for preparing same |
| CN101125677A (en) * | 2007-09-16 | 2008-02-20 | 中国日用化学工业研究院 | Method for preparing high dispersity nano zinc oxide |
| CN101960603A (en) * | 2008-01-08 | 2011-01-26 | 莫克斯特尼克公司 | High-performance heterostructure light emitting devices and methods |
Non-Patent Citations (2)
| Title |
|---|
| APPLIED SURFACE SCIENCE: "Electrical and optical properties of Al-doped ZnO thin films by sol–gel process", 《APPLIED SURFACE SCIENCE》 * |
| 闵惠玲等: "纳米氧化锌表面改性及应用研究", 《印染》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11495766B2 (en) | 2019-10-24 | 2022-11-08 | Samsung Electronics Co., Ltd. | Electroluminescent device, and display device comprising thereof |
| US11871594B2 (en) | 2019-10-24 | 2024-01-09 | Samsung Electronics Co., Ltd. | Electroluminescent device, and display device comprising thereof |
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