CN106299159B - The preparation method and quanta point electroluminescent device of metal oxide nanoparticles - Google Patents
The preparation method and quanta point electroluminescent device of metal oxide nanoparticles Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of metal oxide nanoparticles and quanta point electroluminescent devices.Above-mentioned preparation method includes：Under the atmosphere of nitrogen or inert gas, mixture comprising metal precursor, reducing agent and organic solvent is heated, obtain metal oxide nanoparticles, wherein, metal oxide nanoparticles include the surface ligand of metal oxide and the metal oxide formed by reducing agent, metal precursor is one or more in the group that molybdenum salt, tungsten salt and vanadic salts form, and reducing agent is selected from unsaturated fatty acid and/or unsaturated fat amine.There is size tunable using metal oxide nanoparticles made from preparation method provided by the present application, the features such as homogeneity is good and good dispersion.
Description
Technical field
The present invention relates to quantum dot light emitting fields, in particular to a kind of preparation side of metal oxide nanoparticles
Method and quanta point electroluminescent device.
Background technology
QLED becomes next-generation illumination with its unique excellent properties and shows the extremely strong competitor of equipment, existing
The most common structure configuration of QLED devices is ITO/HIL/HTL/QDs/ETL/Al.PEDOT:PSS is due to good conduction
Property, the advantages that lower surface roughness and work content preferable with organic transport layer HOMO energy levels matching, the quilt in QLED
It is widely used as hole injection layer (HIL).
However some reports show PEDOT in recent years:The use of PSS also produces some not to the stability of QLED devices
The influence of profit.PEDOT：PSS has hygroscopicity, after the moisture in absorbing air, while the conductivity of itself declines
Also the service life of QLED devices can be generated and is seriously affected.And due to acid higher (pH value is about 1), PEDOT:PSS will appear
The case where chemistry decays and corrodes ITO electrode.In addition PEDOT:PSS is also proved to be easy to by photooxidation.Disadvantages mentioned above is serious
Influenced the stability of QLED devices, and reduce device lifetime.PEDOT:These undesirable properties of PSS can equally cause
The reduction of itself work content, this can cause to decline with the matching of the HOMO energy levels of organic cavity transmission layer (HTL), to influence
The efficiency of QLED.
In recent years, the inorganic transition metal oxide with good band structure and stability, such as MoO3、V2O5、
NiO and WO3Deng, be already used to substitute PEDOT:PSS is as hole injection layer material.Especially MoO3, it is not only a kind of nothing
The material of poison, and with the electronic state compared with deep energy level, (vacuum deposition is WF=6.7eV, exposes WF=when in air
5.7eV), thus MoO3It is that one kind gets a good chance of replacing PEDOT:The hole injection layer material of PSS.These inorganic, metal oxides
It can be deposited by a variety of methods, including thermal evaporation, electron beam evaporation, sputtering and pulse-laser deposition etc., it is contemplated that work
The factors such as skill cost and large-scale production, the above method limit MoO3Application of the equal inorganic, metal oxides in production.It is molten
Although liquid method has the advantages of at low cost, to be capable of the composition ratio of accuracy controlling compound and large-area applications may be implemented,
It is the MoO that existing solwution method is synthesized3There are grain diameter is uneven and easy the shortcomings of reuniting.Pass through spin coating mode
The film of deposition will appear more coarse phenomenon, leads to the leakage of current for occurring larger, seriously affects device performance
Raising.
Invention content
The main purpose of the present invention is to provide a kind of preparation method of metal oxide nanoparticles and quantum dot are electroluminescent
Luminescent device, to solve the problems, such as metal oxide made from existing solwution method, there are grain size is uneven and easy reunite.
To achieve the goals above, one aspect of the invention provides a kind of preparation side of metal oxide nanoparticles
Method, preparation method include：Under the atmosphere of nitrogen or inert gas, metal precursor, reducing agent and organic solvent will be included
Mixture is heated, and metal oxide nanoparticles are obtained, wherein metal oxide nanoparticles include metal oxide and
By the surface ligand for the metal oxide that reducing agent is formed, metal precursor is in the group that molybdenum salt, tungsten salt and vanadic salts form
One or more, reducing agent is selected from unsaturated fatty acid and/or unsaturated fat amine.
Further, the process of heating includes：First heating process heats the mixture to 100~130 DEG C, constant temperature 20
~30min；And second heating process, mixture is continued to be heated to 200~300 DEG C, 30~300min of constant temperature, preferably second plus
The temperature of thermal process is 250~290 DEG C, and 60~120min of constant temperature obtains metal oxide nanoparticles.
Further, a concentration of 0.01~1mmol/mL of reducing agent in organic solvent, preferably 0.1mmol~
0.8mmol/mL。
Further, metal precursor and the molar ratio of reducing agent are 1:1~1:100, preferably 1:5~1:75.
Further, the one kind or more of organic solvent in the group that octadecylene, paraffin, diphenyl ether and dioctyl ether form
Kind.
Further, aliphatic acid is selected from oleic acid and/or lauroleic acid；Preferably, fatty amine is oleyl amine, octylame and lauryl amine
It is one or more in the group of composition.
Further, molybdenum salt is one or more in the group that ammonium heptamolybdate, ammonium tetramolybdate and ammonium dimolybdate form；It is excellent
Selection of land, tungsten salt are one or more in the group that ammonium tungstate, ammonium paratungstate and ammonium metatungstate form；Preferably, vanadic salts is inclined
Ammonium vanadate and/or ammonium poly-vanadate.
Further, above-mentioned preparation method further includes that metal oxide nanoparticles and hydrophilic ligand are carried out ligand friendship
The step of changing.
Further, hydrophilic ligand is selected from dissolvable sulfide, metal chalcogenide, carboxyl type organic and amine and has
It is one or more in the group of machine object composition；Preferably, dissolvable sulfide is selected from ammonium sulfide, potassium sulfide and vulcanized sodium composition
It is one or more in group；Preferably, metal chalcogenide is selected from SnS4 4-、Sn2Se6 4-、Sn2S6 4-、In2Se4 2-Or SnTe4-
It is one or more in the group formed for the compound of anion；Preferably, carboxyl type organic is selected from thioacetic acid, sulfydryl third
It is one or more in acid and the group formed with mercaptohexanoic acid；Preferably, amine organic matter is ethylenediamine and/or hexamethylene diamine.
To achieve the goals above, another aspect of the present invention additionally provides a kind of quanta point electroluminescent device, including sky
Cave implanted layer, the material for forming hole injection layer include functional material, and functional material includes metal oxide nanoparticles, metal
Oxide nano particles are made by above-mentioned preparation method.
Further, the surface ligand of metal oxide nanoparticles is hydrophilic ligand, and functional material further includes poly- 3,
The mixture of 4- ethylenedioxy thiophenes and poly styrene sulfonate.
It applies the technical scheme of the present invention, metal precursor, reducing agent are carried out heating with organic solvent to react and can make
Metal precursor is reduced to metal oxide while reducing agent can also be made to be coordinated with metal oxide surface, this is conducive to
The steric hindrance for increasing metal oxide nanoparticles, to be conducive to inhibit the reunion of metal oxide nanoparticles.Simultaneously
Since the metal oxide nanoparticles formed after being coordinated with reducing agent have certain compatibility with organic solvent, thus will be upper
State the reunion that reaction carries out being conducive to further suppress in organic solvent metal oxide nanoparticles.Based on above-mentioned two aspect
The reason of, have size tunable, homogeneity good using metal oxide nanoparticles made from preparation method provided by the present application
And the features such as good dispersion.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 shows a kind of knot for quantum dot light emitting device that a kind of preferred typical embodiment of the present invention provides
Structure schematic diagram；
Fig. 2 shows the transmission electron microscope pictures of sample obtained in embodiment 2；
Fig. 3 shows the transmission electron microscope picture of sample obtained in embodiment 11；
Fig. 4 shows the transmission electron microscope picture of sample obtained in comparative example 1.
Wherein, above-mentioned attached drawing includes the following drawings label：
10, anode；20, hole injection layer；30, hole transmission layer；40, quanta point electroluminescent layer；50, electron-transport is simultaneous
Implanted layer；60, cathode.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
As described in background technology, there are grain size is uneven and easy hair for metal oxide made from existing solwution method
Raw the problem of reuniting.In order to solve the above technical problem, the present invention provides a kind of preparation sides of metal oxide nanoparticles
Method, the preparation method include：To include metal precursor, reducing agent and organic solvent under the protection of nitrogen or inert gas
Mixture heated, obtain metal oxide nanoparticles, wherein metal oxide nanoparticles include metal oxide
With the surface ligand of the metal oxide formed by reducing agent, metal precursor includes but not limited to molybdenum salt, tungsten salt and vanadic salts group
At group in it is one or more, reducing agent includes but not limited to unsaturated fatty acid and/or unsaturated fat amine.
Metal precursor, reducing agent and organic solvent, which carry out heating, which react, can make metal precursor be reduced to metal to aoxidize
Object can also be such that reducing agent is coordinated with metal oxide surface simultaneously, this is conducive to increase metal oxide nanoparticles
Steric hindrance, to be conducive to inhibit the reunion of metal oxide nanoparticles.Simultaneously because formed after being coordinated with reducing agent
Metal oxide nanoparticles have certain compatibility with organic solvent, thus above-mentioned reaction is had in organic solvent
Conducive to further suppressing the reunion of metal oxide nanoparticles.Based on above-mentioned both sides reason, use is provided by the present application
The features such as metal oxide nanoparticles made from preparation method have size tunable, and homogeneity is good and good dispersion.
In a kind of preferred embodiment, the process of heating includes the first heating process and the second heating process, wherein the
100~130 DEG C are heated the mixture in one heating process, 20~30min of constant temperature；Mixture is continued in second heating process
Until being heated to 200~300 DEG C, 30~180min of constant temperature obtains metal oxide nanoparticles.
The carrying out of first heating process is conducive to the steam by the mixture of metal precursor, reducing agent and organic solvent
Discharge to be conducive to improve the concentration of metal precursor in organic solvent, and then improves in follow-up second heating process
The yield of reaction rate and metal oxide nanoparticles.And the heating temperature of the second heating process and constant temperature time are limited to
The reactivity for being conducive to improve metal precursor and reducing agent in above range, to be conducive to improve metal oxide nano
The yield of particle.
In above-mentioned preparation method, the temperature and time of the second heating process can be adjusted within the above range.One
In kind preferred embodiment, the temperature of the second heating process is 250~290 DEG C, and constant temperature time is 60~120min.Second is added
The temperature and time of thermal process limits the volatilization for advantageously reducing solvent within the above range.
Be conducive to adjust the grain size of metal oxide nanoparticles by adjusting the concentration of reducing agent in organic solvent, and
The dosage for improving reducing agent in a certain range is conducive to improve the controllability of metal oxide nanoparticles grain size.A kind of excellent
In the embodiment of choosing, a concentration of 0.01~1mmol/mL of reducing agent in organic solvent.Concentration of the reducing agent in organic solvent
Including but not limited to above range, but limited and be conducive to further increase metal oxide nanoparticles within the above range
Dispersibility and uniform particle diameter.The preferably a concentration of 0.1~0.8mmol/mL of reducing agent in organic solvent.
In a kind of preferred embodiment, the molar ratio of metal precursor and reducing agent is 1:1~100.Metal precursor
Molar ratio with reducing agent includes but not limited to above range, and the restriction of the molar ratio of the two is conducive to carry within the above range
The yield and dispersibility of high metal oxide nano particles.The molar ratio of preferably metal precursor and reducing agent is 1:5~1:
75.The molar ratio of metal precursor and reducing agent is further limited and is conducive to further improve metal oxygen within the above range
The yield and dispersibility of compound nano particle.
In above-mentioned preparation method, organic solvent commonly used in the art can be selected.It is organic in a kind of preferred embodiment
Solvent includes but not limited to one or more in the group of octadecylene, paraffin, diphenyl ether and dioctyl ether composition.Above-mentioned organic solvent
It is cheap, good with the compatibility of reducing agent to have the characteristics that, thus above-mentioned organic solvent is selected to advantageously reduce metal oxidation
The manufacturing cost of object nano particle, while also helping the dispersibility for further increasing metal oxide nanoparticles.
In a kind of preferred embodiment, fatty acid reduction agent includes but not limited to oleic acid and/or lauroleic acid；It is preferred that
Ground, fatty amine reducing agent include but not limited to one or more in the group of oleyl amine, octylame and lauryl amine composition.Oleic acid, 12
Olefin(e) acid, oleyl amine, octylame and lauryl amine all have longer alkyl segment and good emulsifiability, thus are made using above-mentioned substance
The dispersibility that coordination is conducive to further increase metal oxide nanoparticles is carried out for reducing agent and metal precursor.
In a kind of preferred embodiment, molybdenum salt includes but not limited to ammonium heptamolybdate, ammonium tetramolybdate and ammonium dimolybdate composition
Group in it is one or more；Preferably, tungsten salt includes but not limited in the group that ammonium tungstate, ammonium paratungstate and ammonium metatungstate form
It is one or more；Preferably, vanadic salts includes but not limited to ammonium metavanadate and/or ammonium poly-vanadate.Above-mentioned substance have source it is wide,
The features such as at low cost, thus selection above-mentioned substance advantageously reduces the preparation of metal oxide nanoparticles as metal precursor
Cost.
Above-mentioned metal oxide nanoparticles can be applied to many fields, including quanta point electroluminescent field.
Another aspect of the present invention provides a kind of quanta point electroluminescent device, including hole injection layer, forms the material of hole injection layer
Material includes functional material, and above-mentioned functional material includes the metal oxide nanoparticles made from above-mentioned preparation method.
There is provided metal oxide nanoparticles using the application has size tunable, the spies such as uniform particle diameter and good dispersion
Point, thus the hole injection layer material for being used as quanta point electroluminescent device advantageously reduces the thick of hole injection layer surface
Rugosity, the aggregation and leakage for reducing electric current, and then improve the service life and luminous efficiency of quanta point electroluminescent device.
In another preferred embodiment, above-mentioned preparation method further includes by metal oxide nanoparticles and hydrophily
Ligand carries out the step of ligand exchange.It can be made in aforementioned embodiments by way of carrying out ligand exchange with hydrophilic ligand
Oil-soluble ligand is replaced by hydrophilic ligand some or all of in metal oxide obtained, to but also being handed over through ligand
The metal oxide nanoparticles obtained after changing have certain water-wet behavior；This is also beneficial to prepare according to actual needs oily molten
Property or water soluble metal oxide nano particle, to improve the use value and economic value of the preparation method.
In a kind of preferred embodiment, hydrophilic ligand includes but not limited to dissolvable sulfide, metal chalcogenide chemical combination
It is one or more in the group of object, carboxyl type organic and amine organic matter composition.Preferably, dissolvable sulfide includes but not
It is limited to one or more in the group of ammonium sulfide, potassium sulfide and vulcanized sodium composition；Preferably, metal chalcogenide includes but unlimited
In with SnS44-、Sn2Se64-、Sn2S64-、In2Se42-Or SnTe4-One kind or more in the group formed for the compound of anion
Kind；Preferably, carboxyl type organic includes but not limited to one kind in the group of thioacetic acid, mercaptopropionic acid and mercaptohexanoic acid composition
Or it is a variety of；Preferably, amine organic matter includes but not limited to ethylenediamine and/or hexamethylene diamine.
Further include that metal oxide is received in the actual fabrication process of metal oxide nanoparticles, in above-mentioned preparation method
Preferably suitable acetone, methanol, ethyl alcohol or ethyl acetate etc. is added in metal oxide nanoparticles by the purification process of rice grain
Centrifugation is carried out, is then redissolved (such as n-hexane, normal octane, toluene) in organic solvent.By metal oxide nano
Filter cake is obtained after particle centrifugation, then it is the preservation for being conducive to metal oxide that filter cake, which is dissolved in solvent, simultaneously also
Be conducive to quickly be adjusted to certain concentration when in use.
Another aspect of the present invention provides a kind of quanta point electroluminescent device, as shown in Figure 1, including hole injection layer
20, the material for forming hole injection layer 20 includes functional material, and above-mentioned functional material includes metal made from above-mentioned preparation method
Oxide nano particles.
There is provided metal oxide nanoparticles using the application has size tunable, the spies such as uniform particle diameter and good dispersion
Point.Thus the quanta point electroluminescent device comprising above-mentioned metal oxide nanoparticles is with good stability, shine effect
Rate and longer service life.
In a kind of preferred embodiment, the metal oxide nanoparticles in above-mentioned functional material are that the ligand on surface is
Metal Ion-hydrophilic Ligand, functional material further include the mixture (PEDOT of poly- 3,4-ethylene dioxythiophene and poly styrene sulfonate：PSS).
There is provided metal oxide nanoparticles using the application has size tunable, the spies such as uniform particle diameter and good dispersion
Point.PEDOT is used compared to simple：Materials of the PSS as the hole injection layer 20 of quanta point electroluminescent device, using this Shen
Metal oxide nanoparticles and PEDOT please be provided：It is applied to quantum dot electricity as the material of hole injection layer 20 after PSS doping
Electroluminescence device is conducive to the stability and luminous efficiency that improve quanta point electroluminescent device.
Preferably PEDOT：The doping of PSS and the metal oxide nanoparticles containing hydrophilic ligand is 20 than (weight ratio)
~80:100.By the doping of the two than limiting within the above range, be conducive to further increase quanta point electroluminescent device
Stability and luminous efficiency.
Below in conjunction with specific embodiment, present invention is further described in detail, these embodiments should not be understood as limitation originally
Invent range claimed.
Test method：
The grain size of the metal oxide nanoparticles of embodiment 1 to 12 and comparative example 1 is examined using transmission electron microscope
It surveys.
Embodiment 1
By the ammonium molybdate (NH of 0.4mmol4)6Mo7O24·4H2O, the oleic acid (OA) of 0.2mmol and the organic solvent ten of 20mL
Eight alkene (ODE), which are added in three-necked bottle, obtains mixture；
Under the protection of nitrogen, said mixture is heated to 100 DEG C, constant temperature 30min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 200 DEG C, constant temperature is simultaneously stirred continuously 180min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.
Embodiment 2
By (the NH of 0.4mmol4)6Mo7O24·4H2O, the organic solvent octadecylene of the lauroleic acid of 2mmol and 20mL
(ODE) it is added in three-necked bottle and obtains mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 250 DEG C, constant temperature is simultaneously stirred continuously 100min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.Obtained sample is detected using transmission electron microscope, as a result sees Fig. 2.
Embodiment 3
(the NH of 0.4mmol4)6Mo7O24·4H2O, the oleyl amine (OAM) of the oleic acid (OA) of 3mmol, 7mmol, 20mL's is organic
Solvent octadecylene (ODE), which is added in three-necked bottle, obtains mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 250 DEG C, constant temperature is simultaneously stirred continuously 100min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.
Embodiment 4
(the NH of 0.4mmol4)6Mo7O24·4H2O, the organic solvent octadecylene (ODE) of the lauroleic acid of 20mmol, 40mL
It is added in three-necked bottle and obtains mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 250 DEG C, constant temperature is simultaneously stirred continuously 100min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.
Embodiment 5
(the NH of 0.4mmol4)6Mo7O24·4H2O, the organic solvent octadecylene (ODE) of the oleyl amine (OAM) of 30mmol, 40mL
It is added in three-necked bottle and obtains mixture；
Said mixture is heated to 130 DEG C under the protection of nitrogen, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 290 DEG C, constant temperature is simultaneously stirred continuously 40min and to carry out second adds
Thermal process obtains molybdenum oxide nanoparticles；Be cooled to room temperature, by above-mentioned molybdenum oxide nanoparticles be added acetone in centrifugal analysis with
It is purified.
Embodiment 6
(the NH of 0.4mmol4)6Mo7O24·4H2O, the octylame of 8mmol, 10mL organic solvent octadecylene (ODE) be added to
Mixture is obtained in three-necked bottle；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 250 DEG C, constant temperature is simultaneously stirred continuously 100min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.
Embodiment 7
Under the protection of nitrogen, (the NH of 0.4mmol4)6Mo7O24·4H2O, the oil of the oleic acid (OA) of 10mmol, 30mmol
Amine (OAM), the organic solvent diphenyl ether of 50mL, which is added in three-necked bottle, obtains mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 250 DEG C, constant temperature is simultaneously stirred continuously 100min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.
Embodiment 8
(the NH of 0.4mmol4)6Mo7O24·4H2O, the oleyl amine (OAM) of the oleic acid (OA) of 10mmol, 30mmol, 50mL's has
Solvent dioctyl ether, which is added in three-necked bottle, obtains mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying steam is continued to be heated to 250 DEG C, constant temperature is simultaneously stirred continuously 100min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.
Embodiment 9
The NH of 0.4mmol4VO3, 2mmol oleic acid (OA), the organic solvent octadecylene (ODE) of 20mL is added to three-necked bottle
In obtain mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 30.min is heated for the first time to carry out
Journey empties steam；
Mixture after emptying steam is continued to be heated to 300 DEG C, constant temperature is simultaneously stirred continuously 30min and to carry out second adds
Thermal process obtains vanadium oxide nano particle；Be cooled to room temperature, by above-mentioned vanadium oxide nano particle be added acetone in centrifugal analysis with
It is purified.
Embodiment 10
(the NH of 0.4mmol4)6W7O24·6H2O, the organic solvent octadecylene (ODE) of the oleic acid (OA) of 2mmol, 20mL adds
Enter and obtains mixture into three-necked bottle；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 30.min is heated for the first time to carry out
Journey empties steam；
Mixture after emptying steam is continued to be heated to 300 DEG C, constant temperature is simultaneously stirred continuously 30min and to carry out second adds
Thermal process obtains tungsten oxide nanoparticles；Be cooled to room temperature, by above-mentioned tungsten oxide nanoparticles be added acetone in centrifugal analysis with
It is purified.
Embodiment 11
Mixed liquor and 5mL the 5mg/mL molybdenum oxide made from embodiment 2 of 1mL ammonium sulfide solutions and 4mL formamides is taken to receive
The toluene solution of rice corpuscles is added in the three-necked bottle of 25mL and carries out ligand exchange, and the reaction was complete at room temperature, obtains sulphur ligand
Molybdenum oxide nanoparticles.Obtained sample is detected using transmission electron microscope, as a result sees Fig. 2.
Embodiment 12
On the basis of embodiment 2, the molar ratio of metal precursor and reducing agent is 1:0.5, other conditions and embodiment 2
It is identical.
Comparative example 1
(the NH of 0.4mmol4)6Mo7O24·4H2O, the oleyl amine (OAM) of the oleic acid (OA) of 3mmol, 7mmol is added to three necks
Mixture is obtained in bottle；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out first time heating process,
Empty steam；
Mixture after emptying aqueous vapor is continued to be heated to 250 DEG C, constant temperature is simultaneously stirred continuously 100min to carry out second
Heating process obtains molybdenum oxide nanoparticles；It is cooled to room temperature, centrifugal analysis in acetone is added in above-mentioned molybdenum oxide nanoparticles
To be purified.It is 1.85nm to obtain grain size.Obtained sample is detected using transmission electron microscope, as a result sees Fig. 3.
The grain size of metal nanoparticle obtained is shown in Table 1 in embodiment 1 to 12 and comparative example 1.
Table 1
By embodiment 1 to 12 with comparative example 1 it is found that being added in metal oxide nanoparticles preparation process organic molten
Agent is conducive to improve the controllability and homogeneity of nano particle diameter；By embodiment 1,7 and 8 it is found that by the second heating process
Temperature and heating time limit and advantageously reduce the grain size deviation of nano particle diameter in a certain range, to improve it
Uniform particle diameter；By embodiment 1 and 12 it is found that the concentration restriction of reducing agent is advantageously reduced nanometer in a certain range
The grain size deviation of grain grain size, improves the homogeneity of nano particle；By embodiment 2 and 12 it is found that by metal precursor and reduction
The molar ratio of agent limits the grain size deviation for advantageously reducing nano particle diameter in a certain range, improves the uniform of nano particle
Property.
Simultaneously by Fig. 2 to 4 it is also seen that using metal oxide nanoparticles made from the method in the application
Homogeneity is substantially better than the nano particle prepared using method in comparative example 1.
Embodiment 13
It is shown in FIG. 1 as the material preparation of hole injection layer 20 using molybdenum oxide nanoparticles obtained in embodiment 2
Quanta point electroluminescent device, quanta point electroluminescent device include successively cathode 60 (ITO cathodes), and ZnO nanoparticle is formed
Electron-transport also serve as implanted layer 50, the quanta point electroluminescent layer 40 that red quantum dot is formed, polyvinylcarbazole (PVK) formation
Hole transmission layer 30, molybdenum oxide nanoparticles formed hole injection layer 20, anode 10 (Ag).
Embodiment 14
Using molybdenum oxide nanoparticles obtained in embodiment 11 and poly- (3,4- ethene dioxythiophenes)-polystyrolsulfon acid
(PEDOT:PSS material preparation shown in FIG. 1 quanta point electroluminescent device of the mixture) as hole injection layer 20, wherein
Molybdenum oxide nanoparticles and PEDOT：The weight ratio of PSS is 1:4.
Comparative example 2
On the basis of embodiment 13, using molybdenum oxide nanoparticles obtained in comparative example 1 as hole injection layer 20
Material preparation quanta point electroluminescent device shown in FIG. 1, other conditions are identical as embodiment 13.
Comparative example 3
On the basis of embodiment 14, the material of hole injection layer 20 is PEDOT:PSS, other conditions and 14 phase of embodiment
Together.
Using PR670 spectral luminosities/coloration/radiancy meter of PHOTO RESEARCH companies production, it is in current density
2mA/cm2Under conditions of, test above-described embodiment 13 and 14 and comparative example 1 and 2 electroluminescent device external quantum efficiency
(EQE) and service life.External quantum efficiency is bigger, and luminance is higher.Lifetime testing conditions are 100cd/m2.The electroluminescent hair of quantum dot
The structure of optical device is as shown in Figure 1, its performance is shown in Table 2.
Table 2
By embodiment 13 and 14 with comparative example 2 it is found that being used as sky compared to using nano particle obtained in comparative example 1
Cave implanted layer, the metal oxide nanoparticles prepared using the application are had when preparing electroluminescent device as hole injection layer
Conducive to the external quantum efficiency and service life of raising electroluminescent device；Simultaneously by embodiment 13 and 14 with comparative example 3 it is found that
Compared to using PEDOT：PSS is as hole injection layer material, the metal oxide nanoparticles conduct prepared using the application
Hole injection layer uses itself and PEDOT：When the mixture of PSS is as hole injection layer, be conducive to improve electroluminescent cell
The external quantum efficiency and service life of part.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (20)
1. a kind of preparation method of metal oxide nanoparticles, which is characterized in that the preparation method includes：
Under the atmosphere of nitrogen or inert gas, the mixture comprising metal precursor, reducing agent and organic solvent is added
Heat obtains the metal oxide nanoparticles, wherein the metal oxide nanoparticles include metal oxide and by institute
The surface ligand of the metal oxide of reducing agent formation is stated, the metal precursor is selected from molybdenum salt, tungsten salt and vanadic salts composition
Group in it is one or more, the reducing agent be selected from unsaturated fatty acid and/or unsaturated fat amine,
The process of the wherein described heating includes：
The mixture is heated to 100~130 DEG C, 20~30min of constant temperature by the first heating process；And
Second heating process continues the mixture to be heated to 200~300 DEG C, and 30~300min of constant temperature obtains the metal
Oxide nano particles.
2. preparation method according to claim 1, which is characterized in that in second heating process, by the mixing
Object continues to be heated to 250~290 DEG C, and 60~120min of constant temperature obtains the metal oxide nanoparticles.
3. preparation method according to claim 1, which is characterized in that concentration of the reducing agent in the organic solvent
For 0.01~1mmol/mL.
4. preparation method according to claim 3, which is characterized in that concentration of the reducing agent in the organic solvent
For 0.1mmol~0.8mmol/mL.
5. preparation method according to claim 1, which is characterized in that mole of the metal precursor and the reducing agent
Than being 1:1~1:100.
6. preparation method according to claim 5, which is characterized in that mole of the metal precursor and the reducing agent
Than being 1:5~1:75.
7. preparation method according to claim 1, which is characterized in that the organic solvent is selected from octadecylene, paraffin, hexichol
It is one or more in the group of ether and dioctyl ether composition.
8. preparation method according to claim 1, which is characterized in that the aliphatic acid is selected from oleic acid and/or lauroleic acid.
9. preparation method according to claim 1, which is characterized in that the fatty amine is oleyl amine, octylame and lauryl amine group
At group in it is one or more.
10. preparation method according to claim 1, which is characterized in that the molybdenum salt be selected from ammonium heptamolybdate, ammonium tetramolybdate and
It is one or more in the group of ammonium dimolybdate composition.
11. preparation method according to claim 1, which is characterized in that the tungsten salt be selected from ammonium tungstate, ammonium paratungstate and partially
It is one or more in the group of ammonium tungstate composition.
12. preparation method according to claim 1, which is characterized in that the vanadic salts is ammonium metavanadate and/or more vanadic acid
Ammonium.
13. preparation method according to any one of claim 1 to 12, which is characterized in that the preparation method further includes
The step of metal oxide nanoparticles and hydrophilic ligand are subjected to ligand exchange.
14. preparation method according to claim 13, which is characterized in that the hydrophilic ligand is selected from soluble vulcanize
It is one or more in the group that object, metal chalcogenide, carboxyl type organic and amine organic matter form.
15. preparation method according to claim 14, which is characterized in that the dissolvable sulfide is selected from ammonium sulfide, sulphur
Change one or more in the group of potassium and vulcanized sodium composition.
16. preparation method according to claim 14, which is characterized in that the metal chalcogenide is selected from SnS4 4-、
Sn2Se6 4-、Sn2S6 4-、In2Se4 2-Or SnTe4-It is one or more in the group formed for the compound of anion.
17. preparation method according to claim 14, which is characterized in that the carboxyl type organic be selected from thioacetic acid,
It is one or more in the group of mercaptopropionic acid and mercaptohexanoic acid composition.
18. preparation method according to claim 14, which is characterized in that the amine organic matter be ethylenediamine and/or oneself
Diamines.
19. a kind of quanta point electroluminescent device, including hole injection layer, the material for forming the hole injection layer includes function
Material, the functional material include metal oxide nanoparticles, which is characterized in that the metal oxide nanoparticles are by weighing
Profit requires the preparation method described in any one of 1 to 18 to be made.
20. quanta point electroluminescent device according to claim 19, which is characterized in that the metal oxide nano
The surface ligand of grain is hydrophilic ligand, and the functional material further includes poly- 3,4-ethylene dioxythiophene and polystyrene sulphur
The mixture of hydrochlorate.
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| CN108346749A (en) * | 2017-08-04 | 2018-07-31 | 广东聚华印刷显示技术有限公司 | QLED devices and preparation method thereof |
| CN109370309A (en) * | 2017-09-22 | 2019-02-22 | 苏州星烁纳米科技有限公司 | Composition for ink and electroluminescent device |
| CN109705660A (en) * | 2017-10-25 | 2019-05-03 | Tcl集团股份有限公司 | A kind of compound ink and preparation method thereof, device |
| CN111384245B (en) * | 2018-12-27 | 2021-07-02 | Tcl科技集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN111384306B (en) * | 2018-12-29 | 2021-10-29 | Tcl科技集团股份有限公司 | Preparation method of quantum dot light-emitting diode |
| CN111384270B (en) | 2018-12-29 | 2021-07-30 | Tcl科技集团股份有限公司 | Preparation method of quantum dot light-emitting diode |
| CN110511756B (en) * | 2019-09-23 | 2022-05-13 | 中国科学技术大学先进技术研究院 | Quantum dot material and preparation method and application thereof |
| CN113130796B (en) * | 2020-01-16 | 2022-11-25 | 京东方科技集团股份有限公司 | QLED device, hole transport material, manufacturing method of hole transport material and display device |
| CN113903865B (en) * | 2020-07-06 | 2022-12-06 | Tcl科技集团股份有限公司 | Zinc oxide nano material, preparation method thereof and luminescent device |
| CN115915887A (en) * | 2021-09-30 | 2023-04-04 | Tcl科技集团股份有限公司 | Molybdenum oxide nano material, preparation method thereof, hole functional film and photoelectric device |
| CN115893495A (en) * | 2021-09-30 | 2023-04-04 | Tcl科技集团股份有限公司 | Tungsten oxide nano material and preparation method thereof, hole functional film and photoelectric device |
| WO2023152969A1 (en) * | 2022-02-14 | 2023-08-17 | シャープディスプレイテクノロジー株式会社 | Light-emitting element, quantum dot dispersion solution, display device, method for manufacturing light-emitting element, and method for manufacturing quantum dot dispersion solution |
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