CN110157411A - The preparation method and applications of II-III-V-VI alloy quantum dot - Google Patents
The preparation method and applications of II-III-V-VI alloy quantum dot Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and applications of II-III-V-VI alloy quantum dot, the preparation method, which includes: (1), is mixed to form precursor solution A for the second presoma, the third presoma containing the Vth major element, the 4th presoma containing the VIth major element and the ligand of the first presoma containing the IIth subgroup element, the element containing group-III, precursor solution A is heated, so that precursor solution A reacts to form II-III-V-VI nanocluster complex solution；(2) II-III-V-VI nanocluster complex solution is mixed with activator, reaction obtains II-III-V-VI alloy quantum dot.The present invention is mixed with activator again after four kinds of different forerunner's precursor reactants of activity are formed II-III-V-VI mild nanocluster compound of reactivity, regulate and control the nucleating growth speed and band structure of II-III-V-VI quantum dot by activator, to II-III-V-VI alloy quantum dot for obtaining size and component is uniform, emission defects are few, II-III-V-VI alloy quantum dot fluorescence half-peak width, quantum efficiency are high, can be preferably applied in photoelectric device.
Description
Technical field
The present invention relates to technology of quantum dots fields, preparation method more particularly to II-III-V-VI alloy quantum dot and
It is applied.
Background technique
It is precursor activated too strong due to containing the V such as P in the synthesis of III-V quantum dot such as InP, it is raw to easily lead to non-uniform crystal
Long, wider III-V quantum dot size distribution and wider fluorescence emission peak.In addition, due to radiationless excitonic relaxation process and
The reasons such as unsaturated dangling bond, easily causing the quantum efficiency of intrinsic III-V quantum dot is only 1% or so.In order to improve III-V quantum
The fluorescence quantum yield of point can form III-in II-VI element shell of III-V quantum dot core one layer of greater band gap of outer cladding
V/II-VI core-shell quanta dots, so that the quantum efficiency of III-V/II-VI core-shell quanta dots is promoted to 40% or so.But it should
III-V/II-VI core-shell quanta dots that method is prepared are inhomogenous with size, fluorescence emission peak half-peak is roomy and quantum effect
The low disadvantage of rate.
For this purpose, can improve III-V/II-VI core-shell quanta dots is II-III-V-VI alloy quantum dot.Existing preparation II-
The method of III-V-VI alloy quantum dot includes:
(1), it after mixing four kinds of unitary presomas, boils to pyroreaction and prepares II-III-V-VI quantum dot.The preparation
In method, due to the active difference of each precursors reaction, III precursor and V precursor of high activity, which first react, generates III-V quantum dot, it
II precursor and VI precursor gradually react afterwards, generate similar III-V/II-III-V-VI structure, cause various in single quantum dot
Element composition is inhomogenous, and entire reaction process is easy to produce III-V or II-VI small particles.Therefore, half-peak breadth 40nm~
60nm or more, and the quantum efficiency fluctuation of different fluorescent emissions position is very big.
(2), it boils after mixing II precursor, III precursor and VI precursor to high temperature, reinjects V precursor, pyroreaction is formed
II-III-V-VI quantum dot.In the preparation method, after injecting V precursor at high temperature, III-V is formed with III precursor fast reaction
Quantum dot, II precursor and VI precursor are reacted with III-V quantum dot again, are actually formed III-V/II-VI quantum dot.Therefore, with
Traditional III-V/II-VI core-shell quanta dots are similar, all have the shortcomings that nucleocapsid lattice mismatch degree is high, quantum dot uniformity is poor,
Its fluorescence half-peak breadth is in 42nm~62nm.
(3), after forming II-VI race's molecular cluster by II precursor and VI precursor original position or in advance, before adding III precursor and V
Body, reaction generate II-III-V-VI quantum dot.In the preparation method, although in situ or form II-VI race's molecular cluster in advance,
But need to be added III precursor and V precursor, still it is difficult to avoid that III-V is individually nucleated.Therefore, which is still difficult to
It forms size uniformity and forms uniform alloy quantum dot, product half-peak breadth is unable to satisfy novel display field in 50nm or more
The requirement of narrow half-peak breadth.
Summary of the invention
Based on this, it is necessary in view of the above-mentioned problems, provide a kind of II-III-V-VI alloy quantum dot preparation method and its
Using；The preparation method is using II-III-V-VI mild nanocluster compound of reactivity as polynary presoma, with work
After agent mixing, the nucleating growth speed and band structure of II-III-V-VI quantum dot are regulated and controled by activator, is formed
II-III-V-VI alloy quantum dot more uniform with size.
A kind of preparation method of II-III-V-VI alloy quantum dot, comprising:
(1) by the first presoma containing the IIth subgroup element, the second presoma of the element containing group-III, containing the Vth main group
Third presoma, the 4th presoma containing the VIth major element and the ligand of element are mixed to form precursor solution A, before described
Liquid solution A heating is driven, so that the precursor solution A reacts to form II-III-V-VI nanocluster complex solution；
(2) II-III-V-VI nanocluster complex solution is mixed and heated with activator, reaction obtains II-
III-V-VI alloy quantum dot.
Further, in the precursor solution A, the molar ratio of the Vth major element and group-III element is 0.2:1
~1:1.
Further, in the precursor solution A, the molar ratio of the VIth major element and group-III element is 0.2:1
~2:1.
Further, the ligand include tri octyl phosphine, tributylphosphine, trioctylphosphine amine, dioctylamine, in octylame at least
It is a kind of.
Further, in the precursor solution A, the molar ratio of the ligand and group-III element is 5:1~20:1.
Further, the heating temperature of precursor solution A described in step (1) is 50 DEG C~150 DEG C.
Further, II-III-V-VI nanocluster complex solution includes that InZnPS nanocluster compound is molten
At least one of liquid, InZnPSe nanocluster complex solution.
Further, the activator includes at least one of alkylphosphines, alkylamine, fatty acid.
Further, the group-III member in the activator and II-III-V-VI nanocluster complex solution
The molar ratio of element is 40:1~200:1.
Further, the temperature of heating described in step (2) is 250 DEG C~310 DEG C.
Further, in step (2), solvent is provided, the temperature of the solvent is heated to 250 DEG C~310 DEG C, then by institute
It states II-III-V-VI nanocluster complex solution and is injected in the solvent with the activator and reacted.
Further, step (2) further includes providing precursor solution B, by the precursor solution B and described II-III-
V-VI nanocluster complex solution, activator mixing, reaction obtain II-III-V-VI alloy quantum dot；
Wherein, the precursor solution B includes first presoma, second presoma, the 4th presoma
At least one of.
Further, further comprising the steps of after step (2):
Shell cladding is carried out to II-III-V-VI alloy quantum dot, the shell is the shell containing II-VI element
Layer obtains II-III-V-VI alloy quantum dot with II-VI element shell.
According to another aspect of the invention, a kind of photoelectric device is provided, II-prepared including the preparation method
III-V-VI alloy quantum dot.
In preparation method of the invention, four kinds of different forerunner's precursor reactants of reactivity form II-III-V-VI nanoclusters
Cluster compound, the nanocluster compound contain the Vth as polynary presoma, compared to unitary presoma, especially high activity
The presoma of major element, reactivity are more mild.So then after the nanocluster compound is mixed with activating agent,
The aggregation of nanocluster complex moiety is combined into crystal seed, partially decomposes under the facilitation of activator as polynary presoma
For quantum dot monomer, and to carry out nucleating growth in continued growth to crystal seed.It at the same time, may between single quantum dot monomer
There is also atomic migration process may be also deposited between ion exchange process and similar quantum dot monomer.To pass through activation
Agent regulates and controls the nucleating growth speed and band structure of II-III-V-VI alloy quantum dot, obtains size and component is uniform, luminous
II-III-V-VI few alloy quantum dot of defect.The position of II-III-V-VI alloy quantum dot fluorescence emission peak is 500nm
~580nm, half-peak breadth are 35nm~40nm, and quantum efficiency is 40%~50%.Again by II-III-V-VI alloy quantum dot into
After II-VI element shell of row cladding, the position of fluorescence emission peak is 510nm~600nm, and half-peak breadth is 35nm~40nm, amount
For sub- improved efficiency to 60%~70%, fluorescence half-peak width, quantum efficiency is high, can be preferably applied in photoelectric device to meet
The requirement of the novel narrow half-peak breadth of display field.
Detailed description of the invention
Fig. 1 is among the InZnPS nanocluster complex solution of embodiment 1 and the InZnPS quantum dot synthesis of comparative example 1
The UV absorption spectrogram of process；
Fig. 2 is the electron microscopic picture of the InZnPS nanocluster complex solution of embodiment 1；
Fig. 3 is the electron microscopic picture of the InZnPS alloy quantum dot of embodiment 1；
Fig. 4 is X-ray diffraction (XRD) map of Examples 1 to 2 and comparative example 1~4.
Specific embodiment
The preparation method and applications of II-III-V-VI alloy quantum dot provided by the invention will be made furtherly below
It is bright.Wherein, II-III-V-VI order of elements only indicates that II-III-V-VI alloy quantum dot forms, and does not indicate II-III-V-
VI alloy quantum dot structural order.
Four kinds of different forerunner's precursor reactants of activity are formed II-III-V-VI mild nanocluster of reactivity by the present invention
Compound after the nanocluster compound is mixed as presoma with activator, can regulate and control II-III-V-VI by activator
The nucleating growth speed and band structure of alloy quantum dot, to obtain size and component is uniform, emission defects are few II-
III-V-VI alloy quantum dot, II-III-V-VI alloy quantum dot fluorescence half-peak width, quantum efficiency are high, can preferably answer
For meeting the requirement of the narrow half-peak breadth of novel display field in photoelectric device.
The preparation method of II-III-V-VI alloy quantum dot provided by the invention, comprising:
(1) by the first presoma containing the IIth subgroup element, the second presoma of the element containing group-III, containing the Vth main group
Third presoma, the 4th presoma containing the VIth major element and the ligand of element are mixed to form precursor solution A, before described
Liquid solution A heating is driven, so that the precursor solution A reacts to form II-III-V-VI nanocluster complex solution；
(2) II-III-V-VI nanocluster complex solution is mixed and heated with activator, reaction obtains II-
III-V-VI alloy quantum dot.
In step (1), precursor solution A can carry out initial reaction, the third forerunner including high activity during heating
Body and the second presoma initial reaction are nucleated to form III-V monomer, and the coordination such as the first presoma, the 4th presoma and ligand exists
II-III-V-VI nanocluster compound is integrally formed in III-V monomer surface.Wherein, it is multiple can be enclosed in nanocluster for ligand
The surface for closing object improves its dispersion degree and inhibits the nanocluster compound further combined with to obtain the II-of size uniformity
III-V-VI nanocluster compound.
In addition, the Vth major element of high activity is consumed into III-V amount in II-III-V-VI nanocluster compound
The form of son point monomer is present in II-III-V-VI nanocluster compound, so, the nanocluster compound is as polynary
When presoma, reactivity is more mild relative to unitary presoma, and stability is more preferable, can be with long-time after large scale preparation
Storage, repeatability is more preferable in amplification production.
In some embodiments, the heating temperature of the precursor solution A is 50 DEG C~150 DEG C.Under the heating temperature,
Four kinds of presoma reaction speeds are close, and II-III-V-VI nanocluster compound is formed slowly, so that the nanocluster compound
Middle constituent distribution is more uniform, and in order to be formed in subsequent nucleating growth, size and component are uniform, emission defects are few
II-III-V-VI alloy quantum dot.Preferably, the heating time for controlling precursor solution A is 20 minutes~60 minutes.
In some embodiments, in order to preferably form II-III-V-VI uniform nanocluster compound of constituent,
Need to control the dosage of the Vth major element and the VIth major element in precursor solution A.Preferably, the precursor solution A
In, the molar ratio of the Vth major element and group-III element is 0.2:1~1:1, the VIth major element and group-III element
Molar ratio be 0.2:1~2:1.
In some embodiments, although the IIth subgroup element mainly plays assistant regulating and controlling, in order to make precursor solution A
Preferably form II-III-V-VI nanocluster compound of constituent and size uniformity, the IIth subgroup element and the IIIth master
The molar ratio of race's element is preferably 0.25:1~2:1.
In some embodiments, during forming II-III-V-VI nanocluster compound, in order to preferably inhibit this
The further nucleating growth of nanocluster compound, in the precursor solution A, the molar ratio of the ligand and group-III element
For 5:1~20:1, the ligand includes at least one of tri octyl phosphine, tributylphosphine, trioctylphosphine amine, dioctylamine, octylame.
In the present invention, first presoma includes zinc precursor and cadmium presoma, it is contemplated that cadmium is limited with environmental protection policy
System, so, first presoma is preferably zinc precursor, and the zinc precursor includes zinc acetate, zinc propionate, zinc chloride, bromine
Change at least one of zinc, zinc iodide, zinc polycarboxylate, the carbon chain lengths of the carboxylate radical of the zinc polycarboxylate are more than or equal to 12.
In some embodiments, second presoma includes indium presoma, and the indium presoma includes indium acetate, chlorination
The carbon chain lengths of at least one of indium, indium bromide, indium iodide, Indium Tris acetylacetonate, carboxylic acid indium, the carboxylate radical of the carboxylic acid indium are big
In equal to 12.
In some embodiments, the third presoma includes phosphorus presoma, and the phosphorus presoma includes three (trimethyls
Silicon) phosphorus, three (triethyl group silicon) phosphorus, three (diethylamide) phosphorus, at least one of three (dimethyl amine) phosphorus.
In some embodiments, the 4th presoma includes one of sulphur presoma, selenium presoma, the sulphur forerunner
Body includes at least one of sulphur-octadecylene, three (trimethyl silicane) sulphur, and the selenium presoma includes selenium-octadecylene, three (front threes
At least one of base silicon) selenium.The sulphur presoma and selenium presoma are high activity sulphur presoma and selenium presoma, in alloy amount
Quantum dot nucleating growth can be more participated in when son point nucleating growth, the formation to the Effective Doping and alloy of sulphur, selenium element
There is facilitation.
In some embodiments it is contemplated that using zinc polycarboxylate and carboxylic acid indium as presoma when, in octadecylene equal solvent
In solubility it is more preferable, and generated without the by-products such as acetic acid, so, the zinc precursor is preferably zinc polycarboxylate, before the indium
Driving body is preferably carboxylic acid indium.
In some embodiments, it is also possible to zinc acetate, indium acetate etc. are dissolved in solvent as presoma, then with lauric acid/dodecanoic acid,
Long chain acid of the carbon chain lengths such as tetradecylic acid, hexadecylic acid, stearic acid, oleic acid more than or equal to 12 reacts, and forms zinc polycarboxylate and carboxylic acid indium.
Specifically, step (1) if with indium acetate, inidum chloride, indium bromide, indium iodide, Indium Tris acetylacetonate etc. be indium presoma,
When zinc acetate, zinc propionate, zinc chloride, zinc bromide, zinc iodide etc. are zinc precursor, method are as follows: by indium presoma, zinc precursor
It is dissolved in solvent with long chain acid, the solvent includes that the higher boilings such as the non-coordinating solvent such as octadecylene or octadecane, isotriacontane are molten
Agent, and then 150 DEG C~200 DEG C are warming up to, 20min~60min is reacted, carboxylic acid indium and zinc polycarboxylate are formed with abundant reaction.Later,
Reaction system is down to 50 DEG C hereinafter, one of sulphur presoma, selenium presoma and phosphorus presoma is added, to avoid at high temperature
InP spontaneous nucleation.
So to preferably include InZnPS nanocluster compound molten for II-III-V-VI nanocluster complex solution
At least one of liquid, InZnPSe nanocluster complex solution.
In step (2), after II-III-V-VI mild nanocluster compound of reactivity is mixed with activator, II-
The aggregation of III-V-VI nanocluster complex moiety is combined into crystal seed, another part as polynary presoma activator rush
Quantum dot monomer is decomposed under into effect, and to carry out nucleating growth in continued growth to crystal seed.At the same time, single quantum dot
It is nanocrystalline it is middle may be formed along with the alloying process of ion exchange and form uniform and of uniform size alloy quantum dot, with
And there may be atomic migration process between similar quantum dot nano crystalline substance, allow the size of different quantum dots to be distributed more
It is uniform.To regulate and control the nucleating growth speed and band structure of II-III-V-VI quantum dot by activator, make II-
III-V-VI nanocluster gradates as size and component is uniform, emission defects are few II-III-V-VI alloy quantum dot.
Specifically, the activator mainly at high temperature activates II-III-V-VI nanocluster compound, regulation
II-III-V-VI nanocluster compound is decomposed into monomer and monomer aggregation nucleating growth, to unreacted in precursor solution A
Unitary presoma and activity influence for adjusting alloy quantum dot and supplementing the unitary presoma of addition are smaller.So
In some embodiments, in order to preferably control, II-III-V-VI nanocluster compound is decomposed into quantum dot monomer and monomer is poly-
Collect nucleating growth, the activator rubs with the group-III element in II-III-V-VI nanocluster complex solution
You are than being 40:1~200:1.
In some embodiments, the activator includes at least one of alkylphosphines, alkylamine, fatty acid.Another
In a little embodiments, the alkylphosphines mainly include the alkyl that the alkyl carbon atoms number such as tri octyl phosphine, tributylphosphine is 2~10
Phosphine, the alkylamine mainly include the alkylamine that the alkyl carbon atoms number such as octylame, dioctylamine is 2~10, the fatty acid
The main fatty acid for being 8~22 including carboxylate radicals carbon atom numbers such as oleic acid, capric acid.
In some embodiments, in step (2), the temperature of the reaction is 250 DEG C~310 DEG C.Under the reaction temperature,
It is preferred that the control reaction time is 10min~30min.In view of hot injection method synthesis quantum dot has rapid nucleating growth and alloy
The advantages of change process, the present invention preferably inject II-III-V-VI nanocluster complex solution with the activator molten
In agent, the mixed liquor of the two can also be injected in solvent certainly, the temperature of the solvent is 250 DEG C~310 DEG C, the solvent packet
Include the high boiling solvents such as the non-coordinating solvent such as octadecylene or octadecane, isotriacontane.
In some preferred embodiments, step (2) further include provide precursor solution B, make the precursor solution B with
II-III-V-VI nanocluster complex solution, activator mixing, reaction obtain II-III-V-VI alloy quantum
Point.To which in quantum dot nucleating growth, the presoma in precursor solution B can continue to adjust the element of alloy quantum dot
Composition and nanocrystalline size, to regulate and control band structure and luminous position.
It in view of third presoma activity is too high, cannot be individually added into, so the precursor solution B includes the first forerunner
At least one of body, the second presoma, the 4th presoma.
In some embodiments, the fluorescence for II-III-V-VI alloy quantum dot that preparation method through the invention obtains
The position of emission peak is 500nm~580nm, and half-peak breadth is 35nm~40nm, and quantum efficiency is 40%~50%, and particle size is
3.0nm~3.8nm.II-III-V-VI alloy quantum dot size uniformity, fluorescence half-peak width, quantum efficiency are high.
In some preferred embodiments, II-III-V-VI alloy quantum dot include InZnPS alloy quantum dot,
One of InZnPSe alloy quantum dot can replace the sub- point of cadmium content.
In some preferred embodiments, the crystalline substance for II-III-V-VI alloy quantum dot that preparation method of the invention obtains
Lattice constant omits between the lattice constant of III-V structure and the lattice constant of II-VI structure according to element composition is different with ratio
There is difference, but is more nearly with the lattice constant of II-VI structure.So preparation method of the invention obtain II-III-V-VI
Alloy quantum dot can preferably carry out shell cladding, and to be formed, luminescent properties are more preferable, the higher quantum dot of stability.
So further comprising the steps of after step (2): carrying out shell to II-III-V-VI alloy quantum dot
Cladding, the shell are the shell containing II-VI element, obtain II-III-V-VI alloy quantum with II-VI element shell
Point, to improve quantum efficiency.Wherein, II-VI element shell may include ZnS shell.
Specifically, the process of the shell cladding are as follows: by II-III-V-VI alloy quantum dot and the ligand, institute
It states presoma, the presoma for containing the VIth major element containing the IIth subgroup element and is mixed to form mixed liquor, the mixed liquor
It is reacted to obtain containing II-III-V-VI alloy quantum dot with II-VI element shell.
In some preferred embodiments, the molar ratio of the IIth subgroup element and the VIth major element is in the mixed liquor
2:1~1:2.
It is too fast due to easily occurring shell epitaxial growth under high temperature in some preferred embodiments, the non-uniform feelings of shell
Condition, so, in order to form uniform shell cladding, the temperature of the reaction is 230 DEG C~300 DEG C.Under the reaction temperature, instead
It is controllable to 20 minutes~60 minutes between seasonable.
So II-III-V-VI alloy quantum dot that preparation method of the invention obtains can also have II-VI element shell
Layer, and the lattice constant match of II-III-V-VI alloy quantum dot and II-VI structure, covered effect are good.Specifically, having institute
The position for stating the fluorescence emission peak of II-III-V-VI alloy quantum dot of II-VI element shell is 510nm~600nm, half-peak breadth
For 35nm~40nm, quantum efficiency is 60%~70%, and particle size is 4.5nm~5nm.With II-III-V-VI alloy quantum
Point is more preferable compared to luminescent properties, stability is higher.
The present invention also provides a kind of photoelectric device, II-III-V-VI alloy quantum prepared including the preparation method
Point.The photoelectric device includes quantum dot film, quantum dot pipe, quantum stippling film and its closes device, the quantum dot used with LED junction
Light-Emitting Diode.Due to the fluorescence half-peak width of II-III-V-VI alloy quantum dot, quantum efficiency is high, therefore, this Shen
Please photoelectric device luminous efficiency it is high, can preferably meet the requirement of the narrow half-peak breadth of novel display field.
Hereinafter, by the preparation method of II-III-V-VI alloy quantum dot and its being answered by following specific embodiments
With being described further.
Embodiment 1:
By 0.3mmol In (Ac)3(indium acetate), 0.6mmol Zn (Ac)2(zinc acetate), 2.1mmol hexadecylic acid and 12mL
ODE (octadecylene) is added in 100mL three-necked flask, and by the three-necked flask in N2180 DEG C are heated under exhaust condition,
After 180 DEG C of holding 30min, 30 DEG C are down to, adds 0.15mmol TMS-P (three (trimethyl silicane) phosphorus), 0.3mmol S-ODE
Precursor solution A is formed with 1.5mmol TOP (tri octyl phosphine), and then rises to 50 DEG C of reaction 30min, forms InZnPS nanoclusters
Cluster complex solution, it is spare to be down to room temperature.As shown in Figure 1, the InZnPS nanocluster complex solution is in UV absorption spectrogram
Start to lift at middle 400nm, but without obvious exciton peaks, as shown in Fig. 2, showing InZnPS nanocluster in transmission electron microscope (TEM)
For 1nm or so, illustrate that crystallization is incomplete, is nanocluster composite structure.
15mL octadecylene is added in 50mL three-necked flask, by the three-necked flask in N2300 are heated under exhaust condition
DEG C, the InZnPS nanocluster complex solution of the element of In containing 0.15mmol and the mixed liquor of 6mmol octylame are injected, at 300 DEG C
After keeping 10min, InZnPS alloy quantum dot solution is obtained.Fluorescent emission and transmission are carried out to InZnPS alloy quantum dot solution
Electronic Speculum test, test the data obtained are specifically shown in Table 1, and element composition test result is specifically shown in Table 2.Such as Fig. 3 transmission electron microscope picture
Shown, the average-size of the InZnPS alloy quantum dot is 3.0nm, and size uniformity degree is high, and pattern is preferable.Fig. 3 illustration is single
The high resolution electron microscopy picture of a InZnPS alloy quantum dot, lattice arrangement is orderly uniform, embodies good single-phase alloy
Structure.
Reaction temperature is down to 250 DEG C, 6mL octylame, 1.5mmol Zn are added into InZnPS alloy quantum dot solution
(OA)2(zinc oleate) and 1.5mmol S-TOP (sulphur-tri octyl phosphine), react 30min at 250 DEG C, are down to room temperature and are contained
The product system of the InZnPS alloy quantum dot of ZnS shell.It is extracted with methanol, and is centrifuged with acetone precipitation twice, and will
Precipitating is dissolved in toluene, obtains quantum dot solution, and carry out fluorescent emission and transmissioning electric mirror test, test result is specifically shown in Table
3。
Embodiment 2:
By 0.3mmol In (Ac)3、0.3mmol Zn(Ac)2, 1.5mmol hexadecylic acid and 12mL ODE be added to 100mL tri-
In mouth flask, and by the three-necked flask in N2It is heated to 180 DEG C under exhaust condition, after 180 DEG C of holding 30min, is down to 30 DEG C,
It adds 0.3mmol TMS-P, 0.6mmol S-ODE and 3mmol TBP (tributylphosphine) forms precursor solution A, Jin Ersheng
To 80 DEG C of reaction 30min, InZnPS nanocluster complex solution is formed, it is spare to be down to room temperature.
15mL octadecylene is added in 50mL three-necked flask, by the three-necked flask in N2250 are heated under exhaust condition
DEG C, the InZnPS nanocluster complex solution of the element of In containing 0.15mmol and the mixed liquor of 15mmol dioctylamine are injected,
After 250 DEG C of holding 10min, InZnPS alloy quantum dot solution is obtained.Fluorescent emission is carried out to InZnPS alloy quantum dot solution
And transmissioning electric mirror test, test result are specifically shown in Table 1, element composition test result is specifically shown in Table 2.
Reaction temperature is adjusted to 270 DEG C, 6mL dioctylamine, 3mmol Zn are added into InZnPS alloy quantum dot solution
(OA)2With 1.5mmol S-TOP, 20min is reacted at 270 DEG C.It is down to room temperature and obtains the InZnPS alloy amount containing ZnS shell
The product system of son point.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene twice with methanol, obtained
Quantum dot solution, carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 3.
Embodiment 3:
By 0.3mmol In (Ac)3、0.075mmol Zn(Ac)2, 1.05mmol hexadecylic acid and 12mL ODE be added to
In 100mL three-necked flask, and by the three-necked flask in N2180 DEG C are heated under exhaust condition, after 180 DEG C of holding 30min, drop
To 30 DEG C, adding 0.06mmol TMS-P, 0.06mmol S-TMS (three (trimethyl silicane) sulphur) and 4.5mmol TOA, (three is pungent
Base amine) precursor solution A is formed, and then 50 DEG C of reaction 30min are risen to, InZnPS nanocluster complex solution is formed, is down to
Room temperature is spare.
15mL octadecylene is added in 50mL three-necked flask, by the three-necked flask in N2270 are heated under exhaust condition
DEG C, the InZnPS nanocluster complex solution of the element of In containing 0.1mmol and the mixed liquor of 15mmol oleic acid are injected, at 270 DEG C
After keeping 10min, InZnPS alloy quantum dot solution is obtained.Fluorescent emission and transmission are carried out to InZnPS alloy quantum dot solution
Electronic Speculum test, test result are specifically shown in Table 1.
Reaction temperature is adjusted to 300 DEG C, 6mL octylame, 3mmol Zn (OA) are added into InZnPS alloy quantum dot solution2
With 1.5mmol S-TOP, 40min is reacted at 300 DEG C.It is down to room temperature and obtains the InZnPS alloy quantum dot containing ZnS shell
Product system.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene twice with methanol, obtain quantum
Point solution, carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 3.
Embodiment 4:
By 0.3mmol In (Ac)3、0.6mmol Zn(Ac)2, 2.1mmol hexadecylic acid and 12mL ODE be added to 100mL tri-
In mouth flask, and by the three-necked flask in N2It is heated to 180 DEG C under exhaust condition, after 180 DEG C of holding 30min, is down to 30 DEG C,
It adds 0.15mmol TMS-P, 0.3mmol S-TMS and 6mmol dioctylamine forms precursor solution A, and then rise to 50 DEG C
30min is reacted, InZnPS nanocluster complex solution is formed, it is spare to be down to room temperature.
15mL octadecylene is added in 50mL three-necked flask, by the three-necked flask in N2310 are heated under exhaust condition
DEG C, the InZnPS nanocluster complex solution of the element of In containing 0.05mmol and the mixed liquor of 10mmol capric acid are injected, 310
DEG C keep 30min after, obtain InZnPS alloy quantum dot solution.To InZnPS alloy quantum dot solution progress fluorescent emission and thoroughly
The test of radio mirror, test result are specifically shown in Table 1.
Reaction temperature is adjusted to 300 DEG C, 4mL octylame, 1.5mmol Zn are added into InZnPS alloy quantum dot solution
(OA)2With 1.5mmol S-TOP, 60min is reacted at 300 DEG C.It is down to room temperature and obtains the InZnPS alloy amount containing ZnS shell
The product system of son point.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene twice with methanol, obtained
Quantum dot solution, carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 3.
Embodiment 5:
By 0.3mmol In (Ac)3、0.6mmol Zn(Ac)2, 2.1mmol hexadecylic acid and 12mL ODE be added to 100mL tri-
In mouth flask, and by the three-necked flask in N2It is heated to 180 DEG C under exhaust condition, after 180 DEG C of holding 30min, is down to 30 DEG C.
0.15mmol TMS-P, 0.3mmol S-TMS and 3mmol octylame is added and forms precursor solution A, and then rises to 120 DEG C of reactions
30min forms InZnPS nanocluster complex solution, it is spare to be down to room temperature.
By 0.2mmol In (Ac)3、0.2mmol Zn(Ac)2, 1.0mmol stearic acid and 20mL octadecylene be added to 100mL
In three-necked flask, and by the three-necked flask in N2180 DEG C are heated under exhaust condition, after 180 DEG C of holding 30min, before formation
Drive liquid solution B.Precursor solution B is warming up to 300 DEG C, the InZnPS nanocluster of the injection element of In containing 0.15mmol is multiple
The mixed liquor of polymer solution and 15mmol oleic acid obtains InZnPS alloy quantum dot solution after 300 DEG C of holding 20min.It is right
InZnPS alloy quantum dot solution carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 1.
Reaction temperature is maintained at 300 DEG C, 6mL oleic acid, 1.5mmol Zn are added into InZnPS alloy quantum dot solution
(OA)2With 3mmol S-TOP, 30min is reacted at 300 DEG C.It is down to room temperature and obtains the InZnPS alloy quantum containing ZnS shell
The product system of point.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene, the amount of obtaining twice with methanol
Son point solution, carries out fluorescent emission and transmissioning electric mirror test, is specifically shown in Table 3.
Embodiment 6:
0.3mmol tetradecylic acid indium, 0.6mmol zinc oleate and 12mL ODE are added in 100mL three-necked flask, and should
Three-necked flask is in N2It is heated to 100 DEG C under exhaust condition, after 100 DEG C of holding 10min, is down to 30 DEG C, adds 0.15mmol
TMS-P, 0.3mmol S-ODE and 3mmol TOP form precursor solution A, and then rise to 120 DEG C of reaction 30min, are formed
InZnPS nanocluster complex solution, it is spare to be down to room temperature.
By 0.4mmol In (Ac)3、0.3mmol Zn(Ac)2, 1.8mmol stearic acid and 20mL octadecylene be added to 100mL
In three-necked flask, and by the three-necked flask in N2180 DEG C are heated under exhaust condition, after 180 DEG C of holding 30min, before formation
Drive liquid solution B.Precursor solution B is warming up to 300 DEG C, the InZnPS nanocluster of the injection element of In containing 0.15mmol is multiple
The mixed liquor of polymer solution and 15mmol oleic acid obtains InZnPS alloy quantum dot solution after 300 DEG C of holding 20min.It is right
InZnPS alloy quantum dot solution carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 1.
Reaction temperature is maintained at 300 DEG C, 6mL oleic acid, 1.5mmol Zn are added into InZnPS alloy quantum dot solution
(OA)2With 3mmol S-TOP, 30min is reacted at 300 DEG C.It is down to room temperature and obtains the InZnPS alloy quantum containing ZnS shell
The product system of point.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene, the amount of obtaining twice with methanol
Son point solution, carries out fluorescent emission and transmissioning electric mirror test, is specifically shown in Table 3.
Embodiment 7:
0.3mmol tetradecylic acid indium, 0.6mmol tetradecylic acid zinc and 12mL ODE are added in 100mL three-necked flask, and will
The three-necked flask is in N2It is heated to 100 DEG C under exhaust condition, after 100 DEG C of holding 10min, is down to 30 DEG C.0.15mmol is added
TMS-P, 0.3mmol S-ODE and 3mmol TOP form precursor solution A, and then rise to 150 DEG C of reaction 30min, are formed
InZnPS nanocluster complex solution, it is spare to be down to room temperature.
By 0.6mmol Zn (OA)2, 0.6mmol S-TBP (sulphur-tributylphosphine) is in N2It is mixed under exhaust condition, before formation
Drive liquid solution B.15mL octadecylene is added in 50mL three-necked flask, by the three-necked flask in N2It is heated under exhaust condition
300 DEG C, injection precursor solution B, the InZnPS nanocluster complex solution of the element of In containing 0.15mmol and 15mmol bis- are pungent
The mixed liquor of base amine obtains InZnPS alloy quantum dot solution after 300 DEG C of holding 30min.It is molten to InZnPS alloy quantum dot
Liquid carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 1.
Reaction temperature is down to 270 DEG C, 6mL capric acid, 1.5mmol Zn are added into InZnPS alloy quantum dot solution
(OA)2With 1.5mmol S-TOP, 30min is reacted at 270 DEG C.It is down to room temperature and obtains the InZnPS alloy amount containing ZnS shell
The product system of son point.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene twice with methanol, obtained
Quantum dot solution, carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 3.
Embodiment 8:
0.3mmol hexadecylic acid indium, 0.6mmol zinc oleate and 12mL ODE are added in 100mL three-necked flask, and should
Three-necked flask is in N2It is heated to 100 DEG C under exhaust condition, after 100 DEG C of holding 10min, is down to 30 DEG C, adds 0.15mmol
TMS-P, 0.3mmol S-ODE and 3mmol TOP form precursor solution A, and then rise to 150 DEG C of reaction 30min, are formed
InZnPS nanocluster complex solution, it is spare to be down to room temperature.
By 0.4mmol Zn (OA)2, 0.4mmol S-TOP is in N2It is mixed under exhaust condition, forms precursor solution B.It will
15mL octadecylene is added in 50mL three-necked flask, by the three-necked flask in N2It is heated to 300 DEG C under exhaust condition, injects forerunner
The InZnPS nanocluster complex solution of liquid solution B, In containing 0.15mmol element and the mixed liquor of 15mmol tri octyl phosphine,
After 300 DEG C of holding 30min, InZnPS alloy quantum dot solution is obtained.Fluorescence hair is carried out to InZnPS alloy quantum dot solution
It penetrates and transmissioning electric mirror test, test result is specifically shown in Table 1.
Reaction temperature is down to 250 DEG C, 2mL capric acid, 1.5mmol Zn are added into InZnPS alloy quantum dot solution
(OA)2With 1.5mmol S-TOP, 30min is reacted at 250 DEG C.It is down to room temperature and obtains the InZnPS alloy amount containing ZnS shell
The product system of son point.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene twice with methanol, obtained
Quantum dot solution, carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 3.
Embodiment 9:
0.3mmol hexadecylic acid indium, 0.6mmol hexadecylic acid zinc and 12mL ODE are added in 100mL three-necked flask, and will
The three-necked flask is in N2It is heated to 100 DEG C under exhaust condition, after 100 DEG C of holding 10min, is down to 30 DEG C, adds
0.15mmol TMS-P, 0.3mmol Se-ODE suspension and 3mmol TOP form precursor solution A, and then rise to 50 DEG C instead
30min is answered, InZnPSe nanocluster complex solution is formed, it is spare to be down to room temperature.
15mL octadecylene is added in 50mL three-necked flask, by the three-necked flask in N2300 are heated under exhaust condition
DEG C, the InZnPSe nanocluster complex solution of the element of In containing 0.15mmol and the mixed liquor of 15mmol tri octyl phosphine are injected,
After 300 DEG C of holding 10min, InZnPSe alloy quantum dot solution is obtained.Fluorescence hair is carried out to InZnPS alloy quantum dot solution
It penetrates and transmissioning electric mirror test, is specifically shown in Table 1.
Reaction temperature is down to 230 DEG C, 6mL octylame, 1.5mmol Zn (OA) are added into InZnPSe alloy solution2With
1.5mmol S-TOP reacts 30min at 230 DEG C.It is down to room temperature and obtains the InZnPSe alloy quantum dot containing ZnS shell
Product system.It is extracted, and is centrifuged with acetone precipitation, and precipitating is dissolved in toluene twice with methanol, obtain quantum dot
Solution, carries out fluorescent emission and transmissioning electric mirror test, test result are specifically shown in Table 3.
Comparative example 1:
By 0.3mmol In (Ac)3、0.6mmol Zn(Ac)2, 2.1mmol hexadecylic acid and 12mL ODE be added to 100mL tri-
In mouth flask, and by the three-necked flask in N2It is heated to 180 DEG C under exhaust condition, after 180 DEG C of holding 30min, is down to 30 DEG C,
It adds 0.15mmol TMS-P, 0.3mmol DDT (n- dodecyl mereaptan) and forms a variety of presoma mixed liquors.Again by this it is a variety of before
It drives body mixed liquor and is heated to 300 DEG C of reaction 20min, obtain InZnPS quantum dot solution.In above-mentioned synthesis pilot process, takes and add
The sample of heat to 200 DEG C carries out the test of UV absorption spectrogram (referring to Fig. 1), lifting position about 500nm, and at about 420nm
There is a broad peak region, illustrates InP tentatively at nuclear reaction, nanocrystalline size is larger, and size distributing inhomogeneity.With embodiment
InZnPS nanocluster complex solution in 1 is compared, and the reaction to precursor solution A, formation are received at low temperature in embodiment 1
Rice cluster complex solution, the more conducively control to cluster size and structure.Fluorescent emission is carried out to InZnPS quantum dot solution
And transmissioning electric mirror test, it is specifically shown in Table 1, element composition test result is specifically shown in Table 2.
Reaction temperature is down to 250 DEG C, 6mL octylame, 1.5mmol Zn (OA) are added into InZnPS solution2With
1.5mmol S-TOP reacts 30min at 250 DEG C.It is down to room temperature and obtains the product system containing InZnPS/ZnS.Use methanol
It is extracted, and is centrifuged with acetone precipitation twice, and precipitating is dissolved in toluene, obtain InZnPS/ZnS quantum dot solution,
It carries out fluorescent emission and transmissioning electric mirror test, test result is specifically shown in Table 3.
Comparative example 2:
By 0.3mmol In (Ac)3, 0.9mmol hexadecylic acid, 1mL tri octyl phosphine and 12mL ODE be added to tri- mouthfuls of 100mL
In flask, and by the three-necked flask in N2It is heated to 180 DEG C under exhaust condition, after 180 DEG C of holding 30min, rises to 300 DEG C.
In 300 DEG C of injection 0.15mmol TMS-P, InP quantum dot solution is obtained after reacting 10min.InP quantum dot solution is carried out glimmering
Light emitting and transmissioning electric mirror test, test result are specifically shown in Table 1.
Reaction temperature is down to 250 DEG C, 6mL octylame, 1.5mmol Zn (OA) are added into InP quantum dot solution2With
1.5mmol S-TOP reacts 30min at 250 DEG C.It is down to room temperature and obtains the product system containing InP/ZnS.It is carried out with methanol
It extracts, and is centrifuged with acetone precipitation twice, and precipitating is dissolved in toluene, obtain InP/ZnS quantum dot solution, carry out fluorescence
Transmitting and transmissioning electric mirror test, test result are specifically shown in Table 3, and element composition test result is specifically shown in Table 2.
Comparative example 3:
By 0.3mmol In (Ac)3、0.3mmol Zn(Ac)2, 1.5mmol hexadecylic acid and 12mL ODE be added to 100mL tri-
In mouth flask, and by the three-necked flask in N2It is heated to 180 DEG C under exhaust condition, after 180 DEG C of holding 30min, is added
0.3mmol DDT rises to 300 DEG C.It is molten that InZnPS quantum dot is obtained after 300 DEG C of injection 0.15mmol TMS-P, reaction 10min
Liquid.Fluorescent emission and transmissioning electric mirror test are carried out to InZnPS quantum dot solution, test result is specifically shown in Table 1, element composition
Test result is specifically shown in Table 2.
Reaction temperature is down to 250 DEG C, 6mL octylame, 1.5mmol Zn (OA) are added into InZnPS solution2With
1.5mmol S-TOP reacts 30min at 250 DEG C.It is down to room temperature and obtains the product system containing InZnPS/ZnS.Use methanol
It is extracted, and is centrifuged with acetone precipitation twice, and precipitating is dissolved in toluene, obtain InZnPS/ZnS quantum dot solution,
It carries out fluorescent emission and transmissioning electric mirror test, test result is specifically shown in Table 3.
Comparative example 4:
By 0.6mmol Zn (Ac)2, 1.2mmol hexadecylic acid and 12mL ODE be added in 100mL three-necked flask, and should
Three-necked flask is in N2It is heated to 180 DEG C under exhaust condition, after 180 DEG C of holding 30min, 0.3mmol S-ODE and 5mmol is added
TOP rises to 250 DEG C of reaction 20min, forms ZnS quantum dot solution.Inject 0.2mmol In (Ac) later3、0.1mmol TMS-
The mixed liquor of P and 3mL octylame obtains InZnPS solution after rising to 300 DEG C of holding 10min.InZnPS quantum dot solution is carried out
Fluorescent emission and transmissioning electric mirror test are specifically shown in Table 1, and element composition test result is specifically shown in Table 2.
Reaction temperature is down to 250 DEG C, 6mL octylame, 1.5mmol Zn (OA) are added into InZnPS solution2With
1.5mmol S-TOP reacts 30min at 250 DEG C.It is down to room temperature and obtains the product system containing InZnPS/ZnS.Use methanol
It is extracted, and is centrifuged with acetone precipitation twice, and precipitating is dissolved in toluene, obtain InZnPS/ZnS quantum dot solution,
Fluorescent emission and transmissioning electric mirror test are carried out, is specifically shown in Table 3.
As shown in figure 4, being used to receiving for phenetic analysis Examples 1 to 2 and the InZnPS quantum dot obtained of comparative example 1~4
Rice crystal form and crystal structure.Wherein, black line and dotted lines are respectively the zincblende lattce structure standard card peak of InP and ZnS.Such as
Shown in table 2, analysed for the Elemental Composition of phenetic analysis Examples 1 to 2 and the InZnPS quantum dot obtained of comparative example 1~4,
It is obtained by ICP-AES (inductively coupled plasma atomic emission) test.Wherein list mole of In, Zn, P, S each element
Ratio.
It is higher to can be seen that three of them characteristic peak peak intensity from the InZnPS alloy quantum dot XRD spectra of embodiment 1,
It is higher unimodal for symmetry, and respectively between InP and ZnS base peak, if its main peak (27.4 degree) is in InP main peak (26.3
Degree) and ZnS main peak (28.6 degree) between.This illustrates that InZnPS is similarly zincblende lattce structure, and crystallization degree is higher, alloying compared with
Be it is complete, embody the uniform and uniform alloy structure of structure of composition.Testing its element group by ICP-AES becomes
In0.2Zn0.45P0.15S0.2, with presoma additional proportion In each in synthesis0.22Zn0.45P0.11S0.22It is close, it embodies to alloy amount
The good regulation of sub- point element composition.
It is higher unimodal that embodiment 2 is similarly symmetry, and peak position is slightly displaced from (27.7 degree), embodies and implements
Peak position deviation caused by 1 element of example composition is different.Its element group is tested as In by ICP-AES0.22Zn0.2P0.18S0.4, with conjunction
Each presoma additional proportion In in0.2Zn0.2P0.2S0.4It is close, embody the good regulation to alloy quantum dot element composition.
Comparative example 1 is the InZnPS quantum dot that after mixing In, Zn, P, S presoma prepared by low-temperature-rise to high temperature, and main peak is
Unimodal, the bad judgement of right side hangover, but its secondary peak embodies apparent mixing peak structure (45.9 and 47.2 degree), with InP times
Peak (43.6 degree) and (47.5 degree) of ZnS secondary peak comparisons, illustrate its structure closer to the non-uniform InZnPS/ZnS nucleocapsid knot of structure
Structure is the unimodal of right side hangover after relatively causing mixed peak due to peak position.Testing its element group by ICP-AES becomes
In0.4Zn0.2P0.3S0.1, with presoma additional proportion In each in synthesis0.22Zn0.45P0.11S0.22Differ larger, Zn and S element contains
Measure it is less, this also embody it is more difficult adulterated enter InP lattice in.
Comparative example 2 is InP/ZnS core-shell quanta dots, and peak intensity is weaker, and is presented as mixed peak structure, this demonstrates InP/
ZnS is core-shell quanta dots, and two-phase crystal structure is independent, and crystallization degree is low.Testing its element group by ICP-AES becomes
In0.3Zn0.25P0.2S0.25Although Zn and S constituent content increased, it is distributed in shell, alloy structure can not be formed.
Comparative example 3 is that P presoma high temperature is injected the InZnPS quantum dot that In, Zn, S mix precursor preparation, peak intensity
Spend lower, and peak position, closer to InP, this illustrates it closer to InP/ZnS structure.Its element group is tested by ICP-AES
As In0.4Zn0.1P0.4S0.1, with presoma additional proportion In each in synthesis0.28Zn0.28P0.28S0.16Differ larger, Zn and S member
Cellulose content is less, this also embodies more difficult adulterated and enters in InP lattice.
Comparative example 4 is to be initially formed ZnS quantum dot as crystal seed, then In, P mixing presoma are injected to the InZnPS amount of preparation
Sub-, peak intensity is lower, and XRD main peak is close to mixed peak structure and peak position is closer to ZnS, illustrates that it is tied closer to ZnS/InP
Structure.Its element group is tested as In by ICP-AES0.1Zn0.5P0.1S0.3, with presoma additional proportion each in synthesis
In0.16Zn0.5P0.09S0.25On the low side compared to In content, this embodies this method and is difficult to well regulate and control element composition.
Therefore, the InZnPS quantum dot of InZnPS nanocluster compound preparation of the present invention is alloy structure, and forms member
Element distribution is more uniform, and crystallization degree is high, and bigger difference is distributed in component compared with the various quantum dots of comparative example preparation,
Wherein, the structure that comparative example 4 obtains is more like core-shell structure.
Table 1
Wherein, comparative example 2 is InP quantum dot, and eigen I nP defect is excessive, and fluorescence radiation is very weak, and quantum efficiency is too low, because
The test of this unstressed configuration and quantum efficiency result.
As known from Table 1, the fluorescent emission peak position for II-III-V-VI alloy quantum dot that the embodiment of the present invention is prepared
For 500nm~580nm, half-peak breadth is narrower than comparative example, is 35nm~40nm, and quantum efficiency is higher than comparative example, is 40%~50%,
The requirement of the narrow half-peak breadth of novel display field can be met.
Table 2
Table 3
As known from Table 3, after which being carried out II-VI element shell cladding, quantum efficiency
It is promoted to 60%~70%, can preferably meet the requirement of the narrow half-peak breadth of novel display field.Each skill of embodiment described above
Art feature can be combined arbitrarily, for simplicity of description, not to all possibility of each technical characteristic in above-described embodiment
Combination be all described, as long as being all considered to be this specification note however, there is no contradiction in the combination of these technical features
The range of load.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (14)
1. the preparation method of II-III-V-VI alloy quantum dot of one kind characterized by comprising
(1) by the first presoma containing the IIth subgroup element, the second presoma of the element containing group-III, containing the Vth major element
Third presoma, the 4th presoma containing the VIth major element and ligand be mixed to form precursor solution A, by the presoma
Solution A heating, so that the precursor solution A reacts to form II-III-V-VI nanocluster complex solution；
(2) II-III-V-VI nanocluster complex solution is mixed and heated with activator, reaction obtains II-III-
V-VI alloy quantum dot.
2. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that the forerunner
In liquid solution A, the molar ratio of the Vth major element and group-III element is 0.2:1~1:1.
3. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that the forerunner
In liquid solution A, the molar ratio of the VIth major element and group-III element is 0.2:1~2:1.
4. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that the ligand
Including at least one of tri octyl phosphine, tributylphosphine, trioctylphosphine amine, dioctylamine, octylame.
5. the preparation method of II-III-V-VI alloy quantum dot according to claim 4, which is characterized in that the forerunner
In liquid solution A, the molar ratio of the ligand and group-III element is 5:1~20:1.
6. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that in step (1)
The heating temperature of the precursor solution A is 50 DEG C~150 DEG C.
7. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that described II-
III-V-VI nanocluster complex solution includes InZnPS nanocluster complex solution, InZnPSe nanocluster compound
At least one of solution.
8. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that the activation
Agent includes at least one of alkylphosphines, alkylamine, fatty acid.
9. the preparation method of II-III-V-VI alloy quantum dot according to claim 8, which is characterized in that the activation
The molar ratio of group-III element in agent and II-III-V-VI nanocluster complex solution is 40:1~200:1.
10. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that step (2)
Described in heating temperature be 250 DEG C~310 DEG C.
11. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that step (2)
In, solvent is provided, the temperature of the solvent is heated to 250 DEG C~310 DEG C, then II-III-V-VI nanocluster is answered
Polymer solution is injected in the solvent with the activator and is reacted.
12. the preparation method of II-III-V-VI alloy quantum dot according to claim 1, which is characterized in that step (2)
It further include that precursor solution B is provided, by the precursor solution B and II-III-V-VI nanocluster complex solution, institute
Activator mixing is stated, reaction obtains II-III-V-VI alloy quantum dot；
Wherein, the precursor solution B includes first presoma, second presoma, in the 4th presoma
It is at least one.
13. the preparation method of described in any item II-III-V-VI alloy quantum dots, feature exist according to claim 1~12
In further comprising the steps of after step (2):
Shell cladding is carried out to II-III-V-VI alloy quantum dot, the shell is the shell containing II-VI element, is obtained
To II-III-V-VI alloy quantum dot with II-VI element shell.
14. a kind of photoelectric device, which is characterized in that II-including the described in any item preparation method preparations of claim 1~13
III-V-VI alloy quantum dot.
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|---|---|---|---|---|
| CN105051153A (en) * | 2013-03-15 | 2015-11-11 | 纳米技术有限公司 | Group iii-v/zinc chalcogenide alloyed semiconductor quantum dots |
| CN105378027A (en) * | 2013-03-14 | 2016-03-02 | 纳米技术有限公司 | Quantum dots made using phosphine |
| CN106479482A (en) * | 2016-09-20 | 2017-03-08 | 纳晶科技股份有限公司 | Inp quantum dot and preparation method thereof |
| CN108546553A (en) * | 2018-05-10 | 2018-09-18 | 纳晶科技股份有限公司 | A kind of II-II-VI alloy quantum dots, preparation method and its application |
| CN108659818A (en) * | 2018-06-14 | 2018-10-16 | 嘉兴纳鼎光电科技有限公司 | The synthetic method of quantum dot and the quantum dot of application synthetic method synthesis |
| CN108659817A (en) * | 2018-06-14 | 2018-10-16 | 玻尔兹曼智能科技（苏州）有限公司 | A kind of synthetic method and core-shell quanta dots of core-shell quanta dots |
| CN108893119A (en) * | 2018-07-18 | 2018-11-27 | 纳晶科技股份有限公司 | The preparation method and quantum dot of InP-base alloy quantum dot, device and composition |
| WO2018215396A1 (en) * | 2017-05-23 | 2018-11-29 | Merck Patent Gmbh | Method for synthesizing a semiconducting nanosized material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101664180B1 (en) * | 2010-03-22 | 2016-10-12 | 삼성디스플레이 주식회사 | Method of manufacturing quantum dot |
| CN110746974A (en) * | 2018-07-24 | 2020-02-04 | Tcl集团股份有限公司 | Quantum dot and preparation method thereof |
| CN109337689B (en) * | 2018-09-27 | 2022-03-22 | 纳晶科技股份有限公司 | Doped quantum dot and preparation method thereof |
| CN110157411B (en) * | 2019-06-26 | 2021-07-27 | 纳晶科技股份有限公司 | Preparation method and application of II-III-V-VI alloy quantum dot |
-
2019
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-
2020
- 2020-06-24 WO PCT/CN2020/098251 patent/WO2020259624A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105378027A (en) * | 2013-03-14 | 2016-03-02 | 纳米技术有限公司 | Quantum dots made using phosphine |
| CN105051153A (en) * | 2013-03-15 | 2015-11-11 | 纳米技术有限公司 | Group iii-v/zinc chalcogenide alloyed semiconductor quantum dots |
| CN108048084A (en) * | 2013-03-15 | 2018-05-18 | 纳米技术有限公司 | The semiconductor-quantum-point of group iii-v/zinc alloy of chalkogenide |
| CN106479482A (en) * | 2016-09-20 | 2017-03-08 | 纳晶科技股份有限公司 | Inp quantum dot and preparation method thereof |
| WO2018215396A1 (en) * | 2017-05-23 | 2018-11-29 | Merck Patent Gmbh | Method for synthesizing a semiconducting nanosized material |
| CN108546553A (en) * | 2018-05-10 | 2018-09-18 | 纳晶科技股份有限公司 | A kind of II-II-VI alloy quantum dots, preparation method and its application |
| CN108659818A (en) * | 2018-06-14 | 2018-10-16 | 嘉兴纳鼎光电科技有限公司 | The synthetic method of quantum dot and the quantum dot of application synthetic method synthesis |
| CN108659817A (en) * | 2018-06-14 | 2018-10-16 | 玻尔兹曼智能科技（苏州）有限公司 | A kind of synthetic method and core-shell quanta dots of core-shell quanta dots |
| CN108893119A (en) * | 2018-07-18 | 2018-11-27 | 纳晶科技股份有限公司 | The preparation method and quantum dot of InP-base alloy quantum dot, device and composition |
Non-Patent Citations (1)
| Title |
|---|
| RICHARD P. BROWN 等: "Synthesis and Degradation of Cadmium-Free InP and InPZn/ZnS Quantum Dots in Solution", 《LANGMUIR》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020259624A1 (en) * | 2019-06-26 | 2020-12-30 | 纳晶科技股份有限公司 | Preparation method for ii-iii-v-vi alloy quantum dot and applications thereof |
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