CN106299159A - The preparation method of metal oxide nanoparticles and quanta point electroluminescent device - Google Patents
The preparation method of metal oxide nanoparticles and quanta point electroluminescent device Download PDFInfo
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Abstract
The invention provides preparation method and the quanta point electroluminescent device of a kind of metal oxide nanoparticles.Above-mentioned preparation method includes: under the atmosphere of nitrogen or noble gas, the mixture comprising metal precursor, reducing agent and organic solvent is heated, obtain metal oxide nanoparticles, wherein, metal oxide nanoparticles includes metal-oxide and the surface ligand of metal-oxide formed by reducing agent, one or more in the group of molybdenum salt, tungsten salt and vanadic salts composition of metal precursor, reducing agent is selected from unsaturated fatty acid and/or unsaturated fatty acids amine.The metal oxide nanoparticles that the preparation method using the application to provide prepares has size tunable, and homogeneity is good and the feature such as good dispersion.
Description
Technical field
The present invention relates to quantum dot light emitting field, in particular to the preparation side of a kind of metal oxide nanoparticles
Method and quanta point electroluminescent device.
Background technology
QLED becomes, with the excellent properties of its uniqueness, the competitor that illumination of future generation is the strongest with display device, existing
The configuration of QLED device modal structure is ITO/HIL/HTL/QDs/ETL/Al.PEDOT:PSS is owing to having good conduction
Property, the advantage such as relatively low surface roughness and work content and the organic transport layer HOMO preferable matching of energy level, quilt in QLED
It is widely used as hole injection layer (HIL).
But the stability to QLED device that uses of some reports display PEDOT:PSS also creates some not in recent years
The impact of profit.PEDOT:PSS has hygroscopicity, after the moisture in absorbing air, while the electrical conductivity of itself declines
Also the life-span of QLED device can be produced and have a strong impact on.And due to acidity higher (pH value is about 1), PEDOT:PSS there will be
Chemistry is decayed and corrodes the situation of ITO electrode.In addition PEDOT:PSS is also proved to be easy to by photooxidation.Disadvantages mentioned above is serious
The stability having had influence on QLED device, and reduce device lifetime.These undesirable properties of PEDOT:PSS can cause equally
The reduction of self work content, this can cause the matching of the HOMO energy level with organic cavity transmission layer (HTL) to decline, thus affect
The efficiency of QLED.
In recent years, there is the inorganic transition metal oxide of good band structure and stability, such as MoO3、V2O5、
NiO and WO3Deng, it is already used to substitute PEDOT:PSS as hole injection layer material.Especially MoO3, it is not only a kind of nothing
The material of poison, and (vacuum moulding machine is WF=6.7eV, WF=when exposing in atmosphere to have the electronic state of relatively deep energy level
5.7eV), thus MoO3It it is a kind of hole injection layer material getting a good chance of replacing PEDOT:PSS.These inorganic, metal oxides
Can be deposited by multiple method, 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, said method limits MoO3Deng inorganic, metal oxide application on producing.Molten
Although liquid method has low cost, it is possible to the proportion of composing of accuracy controlling compound and the advantage that large-area applications can be realized, but
It is the MoO that is synthesized of existing solwution method3There is the shortcomings such as the uneven and easy generation reunion of grain diameter.By spin coating mode
The film of deposition there will be the most coarse phenomenon, causes the problems such as bigger leakage of current occur, badly influences device performance
Raising.
Summary of the invention
Present invention is primarily targeted at and provide the preparation method of a kind of metal oxide nanoparticles and quantum dot electroluminescent
Luminescent device, there is the uneven and easy problem occurring to reunite of particle diameter in the metal-oxide prepared to solve existing solwution method.
To achieve these goals, one aspect of the invention provides the preparation side of a kind of metal oxide nanoparticles
Method, preparation method includes: under the atmosphere of nitrogen or noble gas, will comprise metal precursor, reducing agent and organic solvent
Mixture heats, and obtains metal oxide nanoparticles, wherein, metal oxide nanoparticles include metal-oxide and
The surface ligand of the metal-oxide formed by reducing agent, metal precursor is in the group of molybdenum salt, tungsten salt and vanadic salts composition
One or more, reducing agent is selected from unsaturated fatty acid and/or unsaturated fatty acids amine.
Further, the process of heating includes: the first heating process, heats the mixture to 100～130 DEG C, constant temperature 20
～30min；And second heating process, mixture continues to be heated to 200～300 DEG C, constant temperature 30～300min, preferably second adds
The temperature of thermal process is 250～290 DEG C, constant temperature 60～120min, obtains metal oxide nanoparticles.
Further, reducing agent concentration in organic solvent is 0.01～1mmol/mL, preferably 0.1mmol～
0.8mmol/mL。
Further, the mol ratio of metal precursor and reducing agent is 1:1～1:100, preferably 1:5～1:75.
Further, organic solvent one or many in the group of octadecylene, paraffin, diphenyl ether and dioctyl ether composition
Kind.
Further, fatty acid is selected from oleic acid and/or lauroleic acid；Preferably, fatty amine is oleyl amine, octylame and lauryl amine
One or more in the group of composition.
Further, one or more in the group of ammonium heptamolybdate, ammonium tetramolybdate and ammonium dimolybdate composition of molybdenum salt；Excellent
Selection of land, one or more in the group of ammonium tungstate, ammonium paratungstate and ammonium metatungstate composition of tungsten salt；Preferably, vanadic salts is inclined
Ammonium vanadate and/or ammonium poly-vanadate.
Further, above-mentioned preparation method also includes metal oxide nanoparticles and hydrophilic ligand are carried out part friendship
The step changed.
Further, hydrophilic ligand has selected from dissolvable sulfide, metal chalcogenide, carboxyl type organic and amine
One or more in the group of machine thing composition；Preferably, dissolvable sulfide is selected from ammonium sulfide, Potassium monosulfide. and sodium sulfide composition
One or more in group；Preferably, metal chalcogenide is selected from SnS4 4-、Sn2Se6 4-、Sn2S6 4-、In2Se4 2-Or SnTe4-
For one or more in the group that the compound of anion forms；Preferably, carboxyl type organic selected from mercapto acetic acid, sulfydryl third
Acid and and mercaptohexanoic acid composition group in one or more；Preferably, amine Organic substance is ethylenediamine and/or hexamethylene diamine.
To achieve these goals, another aspect of the present invention additionally provides a kind of quanta point electroluminescent device, including sky
Cave implanted layer, the material forming hole injection layer includes that functional material, functional material include metal oxide nanoparticles, metal
Oxide nano particles is prepared by above-mentioned preparation method.
Further, the surface ligand of metal oxide nanoparticles is hydrophilic ligand, and functional material also includes poly-3,
4-ethylenedioxy thiophene and the mixture of poly styrene sulfonate.
Application technical scheme, by metal precursor, reducing agent carries out reacting by heating with organic solvent can make
Metal precursor is reduced to metal-oxide can also make reducing agent be coordinated with metal oxide surface simultaneously, and this is conducive to
Increase the sterically hindered of metal oxide nanoparticles, thus be conducive to suppressing the reunion of metal oxide nanoparticles.Simultaneously
Metal oxide nanoparticles owing to being formed after being coordinated with reducing agent has certain compatibility with organic solvent, thus by upper
State reaction and suppress the reunion of metal oxide nanoparticles the most further.Based on above-mentioned two aspects
Reason, use the application provide preparation method prepare metal oxide nanoparticles there is size tunable, homogeneity is good
And the feature such as good dispersion.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and explanation thereof are used for explaining the present invention, are not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the knot of a kind of quantum dot light emitting device of a kind of the most typical embodiment offer of the present invention
Structure schematic diagram；
Fig. 2 shows the transmission electron microscope picture of the sample prepared in embodiment 2；
Fig. 3 shows the transmission electron microscope picture of the sample prepared in embodiment 11；
Fig. 4 shows the transmission electron microscope picture of the sample prepared in comparative example 1.
Wherein, above-mentioned accompanying drawing includes the following drawings labelling:
10, anode；20, hole injection layer；30, hole transmission layer；40, quanta point electroluminescent layer；50, electric transmission is held concurrently
Implanted layer；60, negative electrode.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Combination mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
As described by background technology, it is uneven and easily send out to there is particle diameter in the metal-oxide that existing solwution method prepares
The raw problem reunited.In order to solve above-mentioned technical problem, the invention provides the preparation side of a kind of metal oxide nanoparticles
Method, this preparation method includes: under the protection of nitrogen or noble gas, will comprise metal precursor, reducing agent and organic solvent
Mixture heat, obtain metal oxide nanoparticles, wherein metal oxide nanoparticles includes 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
One or more in the group become, reducing agent includes but not limited to unsaturated fatty acid and/or unsaturated fatty acids amine.
Metal precursor, reducing agent and organic solvent carry out reacting by heating can make metal precursor be reduced to burning
Thing can also make reducing agent be coordinated with metal oxide surface simultaneously, and this is conducive to increasing metal oxide nanoparticles
Sterically hindered, thus be conducive to suppressing the reunion of metal oxide nanoparticles.Simultaneously because formed after being coordinated with reducing agent
Metal oxide nanoparticles and organic solvent have certain compatibility, thus above-mentioned reaction are had in organic solvent
It is beneficial to suppress further the reunion of metal oxide nanoparticles.Based on above-mentioned both sides reason, the application is used to provide
The metal oxide nanoparticles that preparation method prepares has size tunable, and homogeneity is good and the feature such as good dispersion.
In a kind of preferred embodiment, the process of heating includes the first heating process and the second heating process, wherein, the
One heating process heats the mixture to 100～130 DEG C, constant temperature 20～30min；Mixture is continued by the second heating process
Till being heated to 200～300 DEG C, constant temperature 30～180min, obtain metal oxide nanoparticles.
The carrying out of the first heating process is beneficially by the steam in the mixture of metal precursor, reducing agent and organic solvent
Discharge, thus be conducive to improving metal precursor concentration in organic solvent, and then improve in follow-up second heating process
Reaction rate and the productivity of metal oxide nanoparticles.And heating-up temperature and the constant temperature time of the second heating process are limited to
Be conducive to the reactivity improving metal precursor with reducing agent in above-mentioned scope, thus be conducive to improving metal oxide nano
The productivity of granule.
In above-mentioned preparation method, the temperature and time of the second heating process can be adjusted within the above range.One
Planting in preferred embodiment, the temperature of the second heating process is 250～290 DEG C, and constant temperature time is 60～120min.Add second
The temperature and time of thermal process limits the volatilization advantageously reducing solvent within the above range.
Be conducive to adjusting the particle diameter of metal oxide nanoparticles by regulation reducing agent concentration in organic solvent, and
The consumption improving reducing agent within the specific limits is conducive to improving the controllability of metal oxide nanoparticles particle diameter.Excellent in one
In the embodiment of choosing, reducing agent concentration in organic solvent is 0.01～1mmol/mL.Reducing agent is in the concentration of organic solvent
Include but not limited to above-mentioned scope, but limited and be conducive within the above range improving metal oxide nanoparticles further
Dispersibility and uniform particle diameter.Being preferably reducing agent concentration in organic solvent is 0.1～0.8mmol/mL.
In a kind of preferred embodiment, the mol ratio of metal precursor and reducing agent is 1:1～100.Metal precursor
Include but not limited to above-mentioned scope with the mol ratio of reducing agent, and the mol ratio of the two is limited and is conducive within the above range carrying
The productivity of high metal oxide nanoparticles and dispersibility.The mol ratio being preferably metal precursor and reducing agent is 1:5～1:
75.The mol ratio of metal precursor and reducing agent is limited further and is conducive within the above range further improving metal oxygen
The productivity of compound nano-particle and dispersibility.
In above-mentioned preparation method, organic solvent commonly used in the art can be selected.In a kind of preferred embodiment, organic
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
There is the features such as cheap and reducing agent the compatibility is good, thus select above-mentioned organic solvent to advantageously reduce burning
The preparation cost of thing nano-particle, also helps the dispersibility improving metal oxide nanoparticles further simultaneously.
In a kind of preferred embodiment, fatty acid reduction agent includes but not limited to oleic acid and/or lauroleic acid；Preferably
Ground, fatty amine reducing agent includes 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 are respectively provided with longer alkyl segment and good emulsifiability, thus use above-mentioned substance to make
Carry out coordination for reducing agent and metal precursor and be conducive to improving further the dispersibility of metal oxide nanoparticles.
In a kind of preferred embodiment, molybdenum salt includes but not limited to ammonium heptamolybdate, ammonium tetramolybdate and ammonium dimolybdate composition
Group in one or more；Preferably, during tungsten salt includes but not limited to the group of ammonium tungstate, ammonium paratungstate and ammonium metatungstate composition
One or more；Preferably, vanadic salts includes but not limited to ammonium metavanadate and/or ammonium poly-vanadate.Above-mentioned substance have source wide,
The features such as low cost, thus select above-mentioned substance to advantageously reduce the preparation of metal oxide nanoparticles as metal precursor
Cost.
Above-mentioned metal oxide nanoparticles may apply to a lot of field, 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 functions material includes the metal oxide nanoparticles that prepared by above-mentioned preparation method.
The application is used to provide metal oxide nanoparticles to have size tunable, the spy such as uniform particle diameter and good dispersion
Point, thus the hole injection layer material being used as quanta point electroluminescent device advantageously reduces the thick of hole injection layer surface
Rugosity, the gathering reducing electric current and leakage, and then improve service life and the luminous efficiency of quanta point electroluminescent device.
In another kind of preferred embodiment, above-mentioned preparation method also includes metal oxide nanoparticles and hydrophilic
Part carries out the step of ligand exchange.Can make in aforementioned embodiments by the way of carrying out ligand exchange with hydrophilic ligand
Part or all of oil-soluble part in the metal-oxide prepared is replaced by hydrophilic ligand, thus also makes to hand over through part
The metal oxide nanoparticles obtained after changing has certain water-wet behavior；This is also beneficial to prepare according to actual needs oil soluble
Property or water soluble metal oxide nano-particle, thus improve use value and the economic worth of this preparation method.
In a kind of preferred embodiment, hydrophilic ligand includes but not limited to dissolvable sulfide, metal chalcogenide chemical combination
One or more in the group of thing, carboxyl type organic and amine Organic substance composition.Preferably, dissolvable sulfide include but not
It is limited to one or more in the group of ammonium sulfide, Potassium monosulfide. and sodium sulfide composition；Preferably, metal chalcogenide includes but does not limits
In with SnS44-、Sn2Se64-、Sn2S64-、In2Se42-Or SnTe4-For the one or many in the group that the compound of anion forms
Kind；Preferably, the one during carboxyl type organic includes but not limited to the group of TGA, mercaptopropionic acid and mercaptohexanoic acid composition
Or it is multiple；Preferably, amine Organic substance includes but not limited to ethylenediamine and/or hexamethylene diamine.
In the actual fabrication process of metal oxide nanoparticles, above-mentioned preparation method also including, metal-oxide is received
The purification process of rice grain, preferably adds appropriate acetone, methanol, ethanol or ethyl acetate etc. by metal oxide nanoparticles
Being centrifuged precipitation, then re-dissolved is in organic solvent (such as normal hexane, normal octane, toluene etc.).By metal oxide nano
Obtain filter cake after granule centrifugation, then filter cake is dissolved in solvent the preservation being advantageous for metal-oxide, also simultaneously
Be conducive to the most quickly being adjusted to certain concentration.
Another aspect of the present invention provides a kind of quanta point electroluminescent device, as it is shown in figure 1, include hole injection layer
20, the material forming hole injection layer 20 includes that functional material, above-mentioned functions material include the metal that above-mentioned preparation method prepares
Oxide nano particles.
The application is used to provide metal oxide nanoparticles to have size tunable, the spy such as uniform particle diameter and good dispersion
Point.Thus the quanta point electroluminescent device comprising above-mentioned metal oxide nanoparticles has good stability, luminous effect
Rate and longer service life.
In a kind of preferred embodiment, the metal oxide nanoparticles in above-mentioned functions material is that the part on surface is
Metal Ion-hydrophilic Ligand, functional material also includes the mixture (PEDOT:PSS) of poly-3,4-ethylene dioxythiophene and poly styrene sulfonate.
The application is used to provide metal oxide nanoparticles to have size tunable, the spy such as uniform particle diameter and good dispersion
Point.Use PEDOT:PSS as the material of the hole injection layer 20 of quanta point electroluminescent device compared to simple, use this Shen
After metal oxide nanoparticles please be provided to adulterate with PEDOT:PSS, the materials application as hole injection layer 20 is electric in quantum dot
Electroluminescence device, is conducive to improving stability and the luminous efficiency of quanta point electroluminescent device.
The doping of preferably PEDOT: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 improving further quanta point electroluminescent device
Stability and luminous efficiency.
Being described in further detail the present invention below in conjunction with specific embodiment, these embodiments are it is not intended that limit this
Invent scope required for protection.
Method of testing:
Use transmission electron microscope that the particle diameter of embodiment 1 to 12 and the metal oxide nanoparticles of comparative example 1 is examined
Survey.
Embodiment 1
By the ammonium molybdate (NH of 0.4mmol4)6Mo7O24·4H2The oleic acid (OA) of O, 0.2mmol and the organic solvent ten of 20mL
Eight alkene (ODE) join and obtain mixture in three-necked bottle；
Under the protection of nitrogen, said mixture is heated to 100 DEG C, constant temperature 30min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 200 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 180min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.
Embodiment 2
By (the NH of 0.4mmol4)6Mo7O24·4H2The lauroleic acid of O, 2mmol and the organic solvent octadecylene of 20mL
(ODE) join in three-necked bottle and obtain mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 250 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 100min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.Using transmission electron microscope to detect the sample obtained, result is shown in Fig. 2.
Embodiment 3
(the NH of 0.4mmol4)6Mo7O24·4H2The oleic acid (OA) of O, 3mmol, the oleyl amine (OAM) of 7mmol, 20mL's is organic
Solvent octadecylene (ODE) joins and obtains mixture in three-necked bottle；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 250 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 100min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.
Embodiment 4
(the NH of 0.4mmol4)6Mo7O24·4H2The lauroleic acid of O, 20mmol, the organic solvent octadecylene (ODE) of 40mL
Join and three-necked bottle obtains mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 250 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 100min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.
Embodiment 5
(the NH of 0.4mmol4)6Mo7O24·4H2The oleyl amine (OAM) of O, 30mmol, the organic solvent octadecylene (ODE) of 40mL
Join and three-necked bottle obtains mixture；
Under the protection of nitrogen, said mixture is heated to 130 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 290 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 40min to carry out adding for the second time
Thermal process, obtains molybdenum oxide nanoparticles；Be cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added in acetone centrifugal analysis with
Purify.
Embodiment 6
(the NH of 0.4mmol4)6Mo7O24·4H2The octylame of O, 8mmol, the organic solvent octadecylene (ODE) of 10mL join
Three-necked bottle obtains mixture；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 250 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 100min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.
Embodiment 7
Under the protection of nitrogen, (the NH of 0.4mmol4)6Mo7O24·4H2The oleic acid (OA) of O, 10mmol, the oil of 30mmol
Amine (OAM), the organic solvent diphenyl ether of 50mL joins and obtains mixture in three-necked bottle；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 250 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 100min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.
Embodiment 8
(the NH of 0.4mmol4)6Mo7O24·4H2The oleic acid (OA) of O, 10mmol, the oleyl amine (OAM) of 30mmol, 50mL has
Machine solvent dioctyl ether joins and obtains mixture in three-necked bottle；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 250 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 100min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.
Embodiment 9
The NH of 0.4mmol4VO3, the oleic acid (OA) of 2mmol, the organic solvent octadecylene (ODE) of 20mL joins three-necked bottle
In obtain mixture；
Under the protection of nitrogen, said mixture being heated to 120 DEG C, constant temperature 30.min is the most heated to carry out
Journey, emptying steam；
Continuing to be heated to 300 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 30min to carry out adding for the second time
Thermal process, obtains vanadium oxide nano-particle；Be cooled to room temperature, above-mentioned vanadium oxide nano-particle is added in acetone centrifugal analysis with
Purify.
Embodiment 10
(the NH of 0.4mmol4)6W7O24·6H2The oleic acid (OA) of O, 2mmol, the organic solvent octadecylene (ODE) of 20mL adds
Enter in three-necked bottle, obtain mixture；
Under the protection of nitrogen, said mixture being heated to 120 DEG C, constant temperature 30.min is the most heated to carry out
Journey, emptying steam；
Continuing to be heated to 300 DEG C by the mixture after emptying steam, constant temperature is also stirred continuously 30min to carry out adding for the second time
Thermal process, obtains tungsten oxide nanoparticles；Be cooled to room temperature, above-mentioned tungsten oxide nanoparticles is added in acetone centrifugal analysis with
Purify.
Embodiment 11
Take the molybdenum oxide that mixed liquor and the 5mL 5mg/mL of 1mL ammonium sulfide solution and 4mL Methanamide prepare by embodiment 2 to receive
Carrying out ligand exchange in the three-necked bottle of the toluene solution addition 25mL of rice corpuscles, at room temperature reaction completely, obtains sulfur part
Molybdenum oxide nanoparticles.Using transmission electron microscope to detect the sample obtained, result is shown in Fig. 2.
Embodiment 12
On the basis of embodiment 2, the mol ratio of metal precursor and reducing agent is 1:0.5, other conditions and embodiment 2
Identical.
Comparative example 1
(the NH of 0.4mmol4)6Mo7O24·4H2The oleic acid (OA) of O, 3mmol, the oleyl amine (OAM) of 7mmol joins three necks
Mixture is obtained in Ping；
Under the protection of nitrogen, said mixture is heated to 120 DEG C, constant temperature 20min to carry out for the first time heating process,
Emptying steam；
Continuing to be heated to 250 DEG C by the mixture after emptying aqueous vapor, constant temperature is also stirred continuously 100min to carry out second time
Heating process, obtains molybdenum oxide nanoparticles；It is cooled to room temperature, above-mentioned molybdenum oxide nanoparticles is added centrifugal analysis in acetone
To purify.Obtaining particle diameter is 1.85nm.Using transmission electron microscope to detect the sample obtained, result is shown in Fig. 3.
The particle diameter of the metal nanoparticle prepared in embodiment 1 to 12 and comparative example 1 is shown in Table 1.
Table 1
By embodiment 1 to 12 and comparative example 1, add organic molten in metal oxide nanoparticles preparation process
Agent is conducive to improving controllability and the homogeneity of nano particle diameter；By embodiment 1,7 and 8, by the second heating process
Temperature and advantageously reduce the particle diameter deviation of nano particle diameter in being limited to certain scope heat time heating time, thus improve it
Uniform particle diameter；By embodiment 1 and 12, the concentration of reducing agent is limited and advantageously reduces nanometer within the specific limits
The particle diameter deviation of grain particle diameter, improves the homogeneity of nano-particle；By embodiment 2 and 12, by metal precursor and reduction
The mol ratio of agent limits the particle diameter deviation advantageously reducing nano particle diameter within the specific limits, improves the homogeneous of nano-particle
Property.
Simultaneously by Fig. 2 to 4 it is also seen that use the metal oxide nanoparticles that the method in the application prepares
Homogeneity is substantially better than and uses the nano-particle that in comparative example 1 prepared by method.
Embodiment 13
The molybdenum oxide nanoparticles prepared in employing embodiment 2 is prepared shown in Fig. 1 as the material of hole injection layer 20
Quanta point electroluminescent device, quanta point electroluminescent device includes negative electrode 60 (ITO negative electrode) successively, and ZnO nanoparticle is formed
Electric transmission also serve as implanted layer 50, the quanta point electroluminescent layer 40 that red quantum point is formed, polyvinylcarbazole (PVK) is formed
Hole transmission layer 30, molybdenum oxide nanoparticles formed hole injection layer 20, anode 10 (Ag).
Embodiment 14
Use the molybdenum oxide nanoparticles and poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid prepared in embodiment 11
(PEDOT:PSS) mixture prepares the quanta point electroluminescent device shown in Fig. 1, wherein as the material of hole injection layer 20
Molybdenum oxide nanoparticles is 1:4 with the weight ratio of PEDOT:PSS.
Comparative example 2
On the basis of embodiment 13, use the molybdenum oxide nanoparticles prepared in comparative example 1 as hole injection layer 20
Material prepare the quanta point electroluminescent device shown in Fig. 1, other conditions are identical with embodiment 13.
Comparative example 3
On the basis of embodiment 14, the material of hole injection layer 20 is PEDOT:PSS, other conditions and embodiment 14 phase
With.
PR670 spectral luminosity/colourity/radiancy the meter using PHOTO RESEARCH company to produce, in electric current density be
2mA/cm2Under conditions of, the external quantum efficiency of the electroluminescent device of test above-described embodiment 13 and 14 and comparative example 1 and 2
And service life (EQE).External quantum efficiency is the biggest, and luminance is the highest.Lifetime testing conditions is 100cd/m2.Electroluminescent of quantum dot
The structure of optical device is as it is shown in figure 1, its performance is shown in Table 2.
Table 2
By embodiment 13 and 14 and comparative example 2, compared to using the nano-particle prepared in comparative example 1 as sky
Cave implanted layer, the metal oxide nanoparticles using the application to prepare has when preparing electroluminescent device as hole injection layer
It is beneficial to improve external quantum efficiency and the service life of electroluminescent device；Simultaneously by embodiment 13 and 14 and comparative example 3,
Compared to using PEDOT:PSS as hole injection layer material, use metal oxide nanoparticles conduct prepared by the application
Hole injection layer or when using its mixture with PEDOT:PSS as hole injection layer, is conducive to improving electroluminescent cell
The external quantum efficiency of part and service life.
These are only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art
For Yuan, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (11)
1. the preparation method of a metal oxide nanoparticles, it is characterised in that described preparation method includes:
Under the atmosphere of nitrogen or noble gas, the mixture comprising metal precursor, reducing agent and organic solvent is added
Heat, obtains described metal oxide nanoparticles, and wherein, described metal oxide nanoparticles includes metal-oxide and by institute
Stating the surface ligand of the described metal-oxide that reducing agent is formed, described metal precursor is selected from molybdenum salt, tungsten salt and vanadic salts composition
Group in one or more, described reducing agent be selected from unsaturated fatty acid and/or unsaturated fatty acids amine.
Preparation method the most according to claim 1, it is characterised in that the process of described heating includes:
First heating process, is heated to 100～130 DEG C by described mixture, constant temperature 20～30min；And
Second heating process, continues to be heated to 200～300 DEG C by described mixture, constant temperature 30～300min, and the most described second
The temperature of heating process is 250～290 DEG C, constant temperature 60～120min, obtains described metal oxide nanoparticles.
Preparation method the most according to claim 1 and 2, it is characterised in that described reducing agent is in described organic solvent
Concentration is 0.01～1mmol/mL, preferably 0.1mmol～0.8mmol/mL.
Preparation method the most according to claim 1 and 2, it is characterised in that described metal precursor and described reducing agent
Mol ratio is 1:1～1:100, preferably 1:5～1:75.
Preparation method the most according to claim 1, it is characterised in that described organic solvent is selected from octadecylene, paraffin, hexichol
One or more in the group of ether and dioctyl ether composition.
Preparation method the most according to claim 1, it is characterised in that described fatty acid is selected from oleic acid and/or lauroleic acid；
Preferably, one or more during described fatty amine is the group of oleyl amine, octylame and lauryl amine composition.
Preparation method the most according to claim 1, it is characterised in that described molybdenum salt selected from ammonium heptamolybdate, ammonium tetramolybdate and
One or more in the group of ammonium dimolybdate composition；
Preferably, one or more in the group of ammonium tungstate, ammonium paratungstate and ammonium metatungstate composition of described tungsten salt；
Preferably, described vanadic salts is ammonium metavanadate and/or ammonium poly-vanadate.
Preparation method the most according to any one of claim 1 to 7, it is characterised in that described preparation method also include by
Described metal oxide nanoparticles and hydrophilic ligand carry out the step of ligand exchange.
Preparation method the most according to claim 8, it is characterised in that described hydrophilic ligand selected from dissolvable sulfide,
One or more in the group of metal chalcogenide, carboxyl type organic and amine Organic substance composition；
Preferably, one or more in the group of ammonium sulfide, Potassium monosulfide. and sodium sulfide composition of described dissolvable sulfide；
Preferably, described metal chalcogenide is selected from SnS4 4-、Sn2Se6 4-、Sn2S6 4-、In2Se4 2-Or SnTe4-For anion
One or more in the group of compound composition；
Preferably, described carboxyl type organic selected from mercapto acetic acid, mercaptopropionic acid and mercaptohexanoic acid composition group in one or
Multiple；
Preferably, described amine Organic substance is ethylenediamine and/or hexamethylene diamine.
10. a quanta point electroluminescent device, including hole injection layer, the material forming described hole injection layer includes function
Material, described functional material includes metal oxide nanoparticles, it is characterised in that described metal oxide nanoparticles is by weighing
Profit requires that the preparation method according to any one of 1 to 9 prepares.
11. quanta point electroluminescent devices according to claim 10, it is characterised in that described metal oxide nano
The described surface ligand of grain is hydrophilic ligand, and described functional material also includes poly-3,4-ethylene dioxythiophene and polystyrene sulphur
The mixture of hydrochlorate.
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