CN102212363B - Preparation method of core-shell structure quantum dot - Google Patents
Preparation method of core-shell structure quantum dot Download PDFInfo
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- CN102212363B CN102212363B CN2011100943327A CN201110094332A CN102212363B CN 102212363 B CN102212363 B CN 102212363B CN 2011100943327 A CN2011100943327 A CN 2011100943327A CN 201110094332 A CN201110094332 A CN 201110094332A CN 102212363 B CN102212363 B CN 102212363B
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Abstract
The invention relates to a preparation method of a core-shell structure quantum dot, which belongs to the technical field of nanometer material preparation. The preparation method comprises the following steps of: preparing I-III-VI group nanometer crystal nucleus by using a method for injecting negative ion monomers by using a high temperature oil phase, and preparing one to three layers of II-VI group nanometer crystal shells by using a one-step coupled growth method so as to obtain the quantum dot which takes (CumaAg1-m)x(InnGa1-n)ySz as the nucleus and ZnSe/ZnSepS1-p/Zns as nanometer crystal shells. In the preparation method, the regulation and control on the sizes of nanometer particles are realized through means of changing the concentration and temperature of a system ligand, the proportion of reactants and the like; and the prepared quantum dot has the characteristics of high fluorescent efficiency, good stability, simpleness and convenience for operation, good repeatability, low cost and low toxicity. The prepared quantum dot does not contain heavy metals, not only can meet the requirements of biological markers and biological detection and application, but also provides an excellent luminescent material for illumination, displayers and the like.
Description
Technical field
The invention belongs to the semiconductor nano material preparing technical field.Relate to the quantum dot by the nucleocapsid structure of regulation and control monomer reactivity and the component proportion preparation size is controlled, component is adjustable high fluorescence efficiency, physics and chemistry stable performance.
Background technology
When the size of semiconductor crystal little to a certain extent after (1～20 nanometer), near the electronic level its fermi level is become discontinuous by original quasi-continuous state, this phenomenon is called quantum size effect.Corresponding its character mainly depends on the size of crystal.Typical semiconductor nano is that quantum dot mainly comprises II-VI, III-V and IV-VI family.These quantum dots all show obvious quantum size effect, and its character significantly is different from its body phase material.For example the optical property of quantum dot depends on the size of particle, and it absorbs and emission wavelength changes along with the variation of size.Based on these special performances, semiconductor-quantum-point has important application in fields such as biomarker, illumination, indicating meters.
The research work of colloid semiconductor-quantum-point can be traced back to nineteen eighty-two, Brus group reported first the preparation of water-soluble semiconductor-quantum-point and the research of optical property.After this, some groups have carried out the synthetic and performance study work of semiconductor-quantum-point in succession.
I-III-VI family quantum dot is concerned because it does not contain hypertoxic heavy metal.Compare with typical semiconductor quantum dot such as II-VI, III-V family or IV-VI family quantum dot, the work of synthetic I-III-VI quantum dot is less, and the fluorescence efficiency of current prepared quantum dot is generally lower than 5%, and quantum dot is unstable.For example Castro has reported that in 2003 preparing by the unimolecular reaction precursor method quantum dot size that I-III-VI family quantum dot (Chem.Mater.2003,15,3142-3147)) obtains distributes poor, fluorescence efficiency less than 1%.Along with synthetic development, reported Lu group in 2008 the I-III-VI family quantum dot (Emission in Cubic and six side's phases) for preparing different structure by amine pyrolysis method (amine injects reaction monomers solution), these quantum dot sizes from 5 to 30 nanometers, there is no fluorescent emission (J.Am.Che.Soc.2008,130,5620-5621).Peng group has reported preparation I-III-VI family quantum dot in 2009.Aspect the improvement fluorescence property, prepare nuclear shell structure quantum point by atomic shell continuous adsorption method (the yin, yang ion alternation adds method), its efficiency can reach 20% (J.Am.Chem.Soc.2009,131,5691-5697) no matter the side's of preparation method, its property research aspect also can't be compared with typical CdSe quantum dot about I-III-VI family quantum dot at present.For example the fluorescence quantum efficiency of CdSe quantum dot can reach more than 80%, and the I-III-VI family quantum dot top efficiency of bibliographical information only has 20% left and right, and quantum dot stability awaits improving.Existing related work mainly concentrates on the I-III-VI family quantum dot (I: III: VI=1: 1: 2) for preparing stoichiometric ratio, while preparing quantum dot, system need to be completed under vacuum condition, quantum dot to some specific dimensions needs size Selection, these methods can be brought inconvenience for quantum dot is synthetic, and for example cost is high, complicated operation.And, to consider from the research aspect of material, the composition of quantum dot and the research of property relationship yet there are no all reports, and from this meaning, the controlled I-III-VI family quantum dot of component for preparing high fluorescence efficiency is the focus of research always.
Summary of the invention
The technical problem to be solved in the present invention is that based on the problem that background technology exists, by regulating and controlling cationic activity, the way of injecting anionic monomer prepares I-III-VI family quantum dot.Obtain first by regulation and control monomer composition and temperature the I-III-VI family quantum dot that size is controlled, component is adjustable.Further experiment shows, it is that the composition of quantum dot is closely related with its fluorescence efficiency that the quantum dot of different components shows different optical properties.The present invention in the experiment for preparing shell, uses the symbiosis regular way to prepare the core-shell structure quantum dot, and the quantum dot of acquisition has high fluorescence efficiency.This method is simple to operate, and is with low cost, is easy to enlarge scale production.
The nuclear shell structure quantum point that forms of differing materials that the present invention is based on the energy band engineering the Theory Construction, the I-III-VI family quantum dot that uses the symbiosis regular way to prepare composite shell not only has satisfactory stability, and its fluorescence efficiency can reach more than 60%.Utilize the I-III-VI family quantum dot of method preparation of the present invention can replace typical CdSe quantum dot fully from the optical property aspect, substantially can meet the field application demands such as biomarker, illumination and indicating meter.
The quantum dot of the present invention's preparation is comprised of I-III-VI family quantum dot core and II-VI family quantum dot shell two portions.The material that forms these nanocrystal does not all contain the heavy metal element of severe toxicity.Concrete quantum dot core is (Cu
mAg
1-m)
x(In
nGa
1-n)
yS
z, 1＜x≤11,1＜y≤11 wherein, z is along with x and y numerical value change and change, and z=(x+3y)/2 is to meet the valent requirement of molecule; That is, I family element is copper or/and silver, and copper and silver-colored mol ratio are 1-m/m, 1 〉=m 〉=0; The III group element is indium or/and gallium, and indium and gallium mol ratio are 1-n/n, 1 〉=n 〉=0; VI family element is sulphur.Concrete quantum dot shell is Zn (S
pSe
1-p) namely, II family element is zinc, VI family element is sulphur or/and selenium, and sulphur and selenium mol ratio are 1-p/p, 1 〉=p 〉=0; The quantum dot shell can have 1～3 layer, and the shell thickness of differing materials is adjustable; The quantum dot shell comprises: ZnS, ZnSe, ZnSe
pS
1-p, ZnSe/ZnS and ZnSe/ZnSe
pS
1-p/ ZnS.
As shown in Figure 1, the present invention prepares I-III-VI family quantum dot core by regulation and control cationic monomer activity, injection negatively charged ion precursor methods.Different cationic monomers and different mercaptos alcohol form title complex,, by adding the monomer of different ratios, inject at a certain temperature anionic monomer and can obtain I-III-VI family quantum dot core.Prepare by the symbiosis regular way for the quantum dot shell.The symbiosis regular way is exactly that the material of growth shell is mixed together the method that adds the growth quantum point shell.The mix monomer of Shell Materials injects in low temperature, heated solution prepares shell to higher temperature subsequently, symbiosis length is once the thickness B1 layer as shown in Figure 1 of an individual molecule layer material, then adds the repetitive operation of differing materials monomer can prepare respectively B2 layer and B3 layer.This method is simple and be easy to the composition of refining shell thickness and material.The work of background technology, as J.Am.Chem.Soc.2009,131,5691-5697, be mainly that S and Zn are alternately added, and do not add suitable part, as mercapto alcohol etc., and reaction must be carried out at vacuum condition.And symbiosis method of the present invention not only can scale operation, and easy and simple to handle, the more important thing is that there is suitable ligand passive quantum dot surface on the core-shell particles surface that obtains, thereby the quantum dot that obtains has higher fluorescence efficiency.
The preparation method's of concrete nuclear shell structure quantum point technical scheme is as follows:
A kind of preparation method of nuclear shell structure quantum point, described nuclear shell structure quantum point, be with I
x-III
y-S
((x+3y)/2)For quantum dot core, Zn-VI are that the quantum dot shell forms; Wherein, I family element and III group element mol ratio are x/y, 1≤x≤11,1≤y≤11; I family element is copper or/and silver, and silver is 1-m/m with the copper mol ratio, 1 〉=m 〉=0, and the III group element is indium or/and gallium, and gallium and indium mol ratio are 1-n/n, 1 〉=n 〉=0, VI family element is sulphur or/and selenium, and selenium and sulphur mol ratio are 1-p/p, 1 〉=p 〉=0; The technological process that the coating of the preparation of quantum dot core solution and quantum dot shell is arranged;
The preparation process of described quantum dot core solution is take copper or/and silver-colored cationic monomer, indium or/and gallium cationic monomer, elemental sulfur are raw material, take mercapto alcohol or/and long chain acid as part, take octadecylene, octadecane or icosa alkene as solvent; Copper or/and silver-colored cationic monomer, indium or/and gallium cationic monomer, elemental sulfur feed intake by the quantum dot nuclear consitution; At first with copper or/and silver-colored cationic monomer and part add in the first container, add solvent to be heated to solution clarification and be down to 75～85 ℃, obtain copper or/and the title complex of silver and part; Add indium or/and gallium cationic monomer, part and solvent are heated to the solution clarification in second container, cooling degree to 80 ℃ obtains indium or/and the title complex of gallium and part; Wherein the consumption of part be respectively copper by mol or/and silver-colored cationic monomer or indium or/and 2～5 times of gallium cationic monomer, solvent load by every mmole Cu or/and the cationic monomer of Ag uses 3～50mL; Finally with copper or/and silver and the title complex of part and indium or/and the title complex of gallium and part join in reaction vessel, be heated to 150～250 ℃, the oleyl amine solution that with concentration is the elemental sulfur of 0.8～2 mol/L injects reaction vessel and kept 20 minutes, makes quantum dot core solution;
The coating process of described quantum dot shell is take quantum dot core solution, sulphur or/and the cationic monomer of selenium anionic monomer, zinc as raw material, sulphur or/and the cationic monomer consumption of selenium anionic monomer and zinc feed intake by quantum dot shell component; Sulphur, or/and the cationic monomer of selenium anionic monomer, zinc is dissolved in respectively in oleyl amine, is joined after mixing in the quantum dot core solution of 80～100 ℃; Temperature of reaction is risen to 220～280 ℃ of growth quantum point shells 30～45 minutes; Be down to afterwards room temperature, adding volume ratio is that the mixed solvent of the chloroform of 1: 10 and ethanol makes the quantum dot precipitation, and then centrifugation is distributed to the quantum dot of the nucleocapsid structure that obtains in toluene or normal hexane.
The nuclear shell structure quantum point of the inventive method preparation has satisfactory stability and higher quantum yield.Chemical stability is that after at room temperature placing 6 months, fluorescence efficiency is unchanged.For the quantum dot core of preparation, its efficiency is below 5%.The measurement of quantum yield is calculate to obtain by the contrast rhodamine 6G, and laboratory sample shows by integrating sphere measurement, and the error of efficiency is no more than 5%.The quantum dot efficiency at least 25% of the present invention preparation, optimize the quantum dot efficiency at least 40% of the composition of core, further optimizes quantum dot efficiency that Shell Materials obtains at least more than 60%.Value in the middle of comprising equally for its efficiency of prepared quantum dot.
Quantum dot core, the shell surface ligand of the present invention's preparation are hydrophobic organic molecules, specifically comprise mercapto alcohol, chain alkyl amine or lipid acid, preferred eight alkyl mercapto alcohol, octadecyl mercapto alcohol, stearylamine or oleic acid.
The quantum dot of the inventive method preparation demonstrates good monodispersity, and the size range of core is in the 1-5 nanometer, and shell thickness is between 0.5 to 3.5 nanometer (referring to Fig. 3).The crystalline structure of the quantum dot of preparation is a cube crystalline phase, and is consistent with the Electronic Speculum measuring result by calculating size of particles, shown that prepared quantum dot is by identical forming.
The quantum dot of the inventive method preparation does not contain the heavy metal element of severe toxicity, and by composition and the component of regulation and control quantum dot, its optics emission wavelength has been contained whole visible and near-infrared region (450 to 1000 nanometer).Fig. 2 provides a typical sample CuIn
3S
5And CuIn
3S
5The Absorption and emission spectra of/ZnS core shell structure.
The quantum dot of the inventive method preparation need to regulate and control the cationic monomer activity.The title complex that needs the different positively charged ion of preparation and different mercapto alcohol molecules to form.These cationic monomers comprise zinc acetate, zinc nitrate, zinc octadecanate, neutralized verdigris, cuprous acetate, cupric nitrate, cuprous nitrate, cupric chloride, cuprous chloride, acetylacetone copper, indium acetate, indium chloride, Indium Tris acetylacetonate, Silver Nitrate, gallium chloride and methyl ethyl diketone gallium.Mercapto alcohol has dodecyl mercapto alcohol, eight alkyl mercapto alcohol, octadecyl mercapto alcohol.Prepare the required material of quantum dot and comprise copper, indium, silver, gallium, zinc.Anionic monomer has sulphur and selenium, before the injection anionic monomer, it is dissolved in oleyl amine.
In the complex compound for preparing different parts and monomer, add appropriate lipid acid further to regulate and control size of particles, when for example acid concentration was increased to the solvent equal volume, the size of particles of preparation can reach 15 nanometers, and the ratio of acid and solvent is 1: 10 o'clock, and the size of particle is only 3 nanometers.Long chain acid mainly contains stearic acid, TETRADECONIC ACID and eight acid etc.
The present invention is the standby quantum dot core of oil phase legal system and quantum dot shell, and the solvent of reaction use is non-corrdination type solvent, such as octadecylene, octadecane, icosa alkene etc.Because the quantum dot surface is chain alkyl amine, acid and/or mercapto alcohol, appropriate acetone or ethanol add and cause the quantum dot precipitation, and then are re-dispersed in organic solvent such as toluene or normal hexane equal solvent.In the process of purifying, quantum dot keeps original physics and chemistry performance, and efficiency is constant.
In sum, the characteristics of maximum of the present invention have: 1, and the quantum dot of acquisition has high quantum yield.2, the composition of particle regulates and controls by feed ratio.3, do not need particle is carried out size Selection., 4, reaction does not need to vacuumize, and is simple to operate, more near " green ".
Description of drawings
Fig. 1 is the preparation process schematic diagram of nuclear shell structure quantum point of the present invention.
Fig. 2 is the CuIn that the present invention prepares
3S
5Quantum dot and CuIn
3S
5The Absorption and emission spectra figure of/ZnS core-shell structured quantum dot.
Fig. 3 is the CuIn that the present invention prepares
3S
5The transmission electron microscope photo of/ZnS core-shell structured quantum dot.
Embodiment:
First part: preparation I-III-VI family quantum dot core (embodiment 1～32)
The present invention of being given here has different components I
x-III
y-S
((x+3y)/2)Quantum dot core, x wherein, y are greater than zero any number namely: 11 〉=x 〉=1,11 〉=y 〉=1.It is as follows that the present invention forms the element of I family and III family: I=Cu
mAg
1-mIII=In
nGa
1-nQuantum dot forms can be expressed as (Cu
mAg
1-m)
x(In
nGa
1-n)
yS
((x+3y)/2), m wherein, the numerical value of n is any number between 0 to 1 and comprises 0 and 1. namely: 1 〉=m 〉=0,1 〉=n 〉=0.The molar ratio that method notable feature of the present invention is exactly particle is in full accord with the composition that makes particle.
Embodiment 1:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Cu
4In
2S
5Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to be down to 80 degree after the solution clarification.Add the 0.2mmol indium acetate in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～240 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
4In
2S
5Quantum dot solution.
Embodiment 2:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot Cu
2In
4S
7Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.0.2mmol neutralized verdigris and 0.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol indium acetate, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～240 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
2In
4S
7Quantum dot solution.
Embodiment 3:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot CuInS
2Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol indium acetate, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～240 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes CuInS
2Quantum dot solution.
It is the CuInS for preparing different size that reaction soln is heated to
2Quantum dot.
Embodiment 4:
Work as m=1, n=0.5, the synthetic quantum dot of typical case is Cu
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Cu
4InGaS
5Synthetic example is as follows:
At first the title complex for preparing copper, indium, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.1mmol indium acetate, 0.1mmol acetic acid gallium in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to rear cooling degree to 80 degree of solution clarification with this solution.The mercapto of copper, gallium and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
4InGaS
5Quantum dot solution.
Embodiment 5:
Work as m=1, n=0.5, the synthetic quantum dot of typical case is Cu
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot Cu
2In
2Ga
2S
7Synthetic example is as follows:
At first the title complex for preparing copper, indium, gallium and mercapto alcohol.0.2mmol neutralized verdigris and 0.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.2mmol indium acetate, 0.2mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper, gallium and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
2In
2Ga
2S
7Quantum dot solution.
Embodiment 6:
Work as m=1, n=0.5, the synthetic quantum dot of typical case is Cu
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot Cu
2InGaS
4Synthetic example is as follows:
At first the title complex for preparing copper, indium, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol indium acetate, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 120 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper, gallium and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
2InGaS
4Quantum dot solution.
Embodiment 7:
Work as m=1, n=0, the synthetic quantum dot of typical case is Cu
xGa
yS
((x+3y)/2), wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Cu
4Ga
2S
5Synthetic example is as follows:
At first the title complex for preparing copper, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.2mmol acetic acid gallium in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
4Ga
2S
5Quantum dot solution.
Embodiment 8:
Work as m=1, n=0, the synthetic quantum dot of typical case is Cu
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot Cu
2Ga
4S
7Synthetic example is as follows:
At first the title complex for preparing copper, gallium and mercapto alcohol.0.2mmol neutralized verdigris and 0.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
2Ga
4S
7Quantum dot solution.
Embodiment 9:
Work as m=1, n=0, the synthetic quantum dot of typical case is Cu
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot CuGaS
2Synthetic example is as follows:
At first the title complex for preparing copper, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes CuGaS
2Quantum dot solution.
Embodiment 10:
Work as m=0.5, n=1, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Ag
2Cu
2In
2S
5Synthetic example is as follows:
At first prepare the title complex of silver, copper, indium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add the 0.2mmol indium acetate in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Ag
2Cu
2In
2S
5Quantum dot solution.
Embodiment 11:
Work as m=0.5, n=1, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot AgCuIn
4S
7Synthetic example is as follows:
At first prepare the title complex of silver, copper, indium and mercapto alcohol.0.1mmol Silver monoacetate, 0.1mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add the 0.4mmol indium acetate in another flask, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes AgCuIn
4S
7Quantum dot solution.
Embodiment 12:
Work as m=0.5, n=1, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot AgCuGa
2S
4Synthetic example is as follows:
At first prepare the title complex of silver, copper, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes CuGaS
2Quantum dot solution.
Embodiment 13
Work as m=0.5, n=0.5, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Ag
2Cu
2InGaS
5Synthetic example is as follows:
At first prepare the title complex of silver, copper, indium, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.1mmol indium acetate, the 0.1mmol acetic acid gallium 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper, indium and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Ag
2Cu
2InGaS
5Quantum dot solution.
Embodiment 14
Work as m=0.5, n=0.5, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot AgCuIn
2Ga
2S
7Synthetic example is as follows:
At first prepare the title complex of silver, copper, indium, gallium and mercapto alcohol.0.1mmol Silver monoacetate, 0.1mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.2mmol indium acetate, 0.2mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper, indium and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 ℃, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes AgCuIn
2Ga
2S
7Quantum dot solution.
Embodiment 15:
Work as m=0.5, n=0.5, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot AgCuGaInS
4Synthetic example is as follows:
At first prepare the title complex of silver, copper, indium, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.2mmol acetic acid gallium, 0.2mmol indium acetate, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper, indium and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes AgCuGaInS
4Quantum dot solution.
Embodiment 16:
Work as m=0.5, n=0, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Cu
2Ag
2Ga
2S
5Synthetic example is as follows:
At first the title complex for preparing copper, indium gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.2mmol acetic acid gallium in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Cu
2Ag
2Ga
2S
5Quantum dot solution.
Embodiment 17:
Work as m=0.5, n=0, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot CuAgGa
4S
7Synthetic example is as follows:
At first the title complex for preparing copper, silver-colored gallium and mercapto alcohol.0.1mmol Silver monoacetate, 0.1mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes CuAgGa
4S
7Quantum dot solution.
Embodiment 18:
Work as m=0.5, n=0, the synthetic quantum dot of typical case is (Ag
0.5Cu
0.5)
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot AgCuGa
2S
4Synthetic example is as follows:
At first prepare the title complex of silver, copper, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, copper and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes AgCuGa
2S
4Quantum dot solution.
Embodiment 19:
Work as m=0, n=1, the synthetic quantum dot of typical case is Ag
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Ag
4In
2S
5Synthetic example is as follows:
At first prepare the title complex of silver, indium and mercapto alcohol.0.4mmol Silver monoacetate and 0.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add the 0.2mmol indium acetate in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of silver and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Ag
4In
2S
5Quantum dot solution.
Embodiment 20:
Work as m=0, n=1, the synthetic quantum dot of typical case is Ag
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot Ag
2In
4S
7Synthetic example is as follows:
At first prepare the title complex of silver, indium and mercapto alcohol.0.2mmol Silver monoacetate and 0.2mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol indium acetate, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Ag
2In
4S
7Quantum dot solution.
Embodiment 21:
Work as m=0, n=1, the synthetic quantum dot of typical case is Ag
xIn
yS
((x+3y)/2), wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot AgInS
2Synthetic example is as follows:
At first prepare the title complex of silver, indium and mercapto alcohol.0.4mmol Silver monoacetate and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol indium acetate, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes AgInS
2Quantum dot solution.
Embodiment 22:
Work as m=0, n=0.5, the synthetic quantum dot of typical case is Ag
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Ag
4InGaS
5Synthetic example is as follows:
At first prepare the title complex of silver, indium, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.1mmol indium acetate, 0.1mmol acetic acid gallium in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, gallium and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Ag
4InGaS
5Quantum dot solution.
Embodiment 23:
Work as m=0, n=0.5, the synthetic quantum dot of typical case is Ag
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot Ag
2In
2Ga
2S
7Synthetic example is as follows:
At first prepare the title complex of silver, indium, gallium and mercapto alcohol.0.2mmol Silver monoacetate and 0.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.2mmol indium acetate, 0.2mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, gallium and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Ag
2In
2Ga
2S
7Quantum dot solution.
Embodiment 24:
Work as m=0, n=0.5, the synthetic quantum dot of typical case is Ag
x(In
0.5Ga
0.5)
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot Ag
2InGaS
4Synthetic example is as follows:
At first prepare the title complex of silver, indium, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol indium acetate, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver, gallium and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes Ag
2InGaS
4Quantum dot solution.
Embodiment 25:
Work as m=0, n=0, the synthetic quantum dot of typical case is Ag
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Ag
4Ga
2S
5Synthetic example is as follows:
At first prepare the title complex of silver, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.2mmol acetic acid gallium in another flask, the 0.6mmol eight pure and mild 0.8ml octadecylenes of mercapto, be heated to 150 with this solution and spend to rear cooling degree to 80 degree of solution clarification.The mercapto of silver and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.5mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes.Make Ag
4Ga
2S
5Quantum dot solution.
Embodiment 26:
Work as m=0, n=0, the synthetic quantum dot of typical case is Ag
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot Ag
2Ga
4S
7Synthetic example is as follows:
At first prepare the title complex of silver, gallium and mercapto alcohol.0.2mmol Silver monoacetate and 0.2mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of silver and gallium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.7mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes.Make Ag
2Ga
4S
7Quantum dot solution.
Embodiment 27:
Work as m=0, n=0, the synthetic quantum dot of typical case is Ag
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y=1, a typical quantum dot AgGaS
2Synthetic example is as follows:
At first prepare the title complex of silver, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.4mmol acetic acid gallium, the 1.2mmol eight pure and mild 0.8ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto alcohol title complex of copper silver and gallium is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 0.8mmol elemental sulfur (being dissolved in the 1ml oleyl amine) injects rapidly reaction soln and kept 20 minutes.Make AgGaS
2Quantum dot solution
Embodiment 28:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot core and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot CuIn
11S
17Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.0.1mmol cupric chloride and 0.8mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 140 degree, until be down to 80 degree after the solution clarification.Add 1.1mmol indium acetate, the 3.3mmol eight pure and mild 0.7ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～250 degree, and 1.7mmol elemental sulfur (being dissolved in the 1.5ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes nanocrystal solution.Make CuIn
11S
17Quantum dot solution.
Embodiment 29:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot core and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot CuIn
7S
11Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.0.1mmol cupric nitrate and 0.6mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 130 degree, until be down to 80 degree after the solution clarification.Add 0.7mmol indium acetate, the 2.1mmol eight pure and mild 0.9ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 180～240 degree, and 1.1mmol elemental sulfur (being dissolved in the 1.2ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes nanocrystal solution.Make CuIn
7S
11Quantum dot solution.
Embodiment 30:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot core and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＜1, one a typical quantum dot CuIn
5S
8Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.0.1mmol cuprous acetate and 0.2mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 130 degree, until be down to 80 degree after the solution clarification.Add 0.5mmol indium acetate, the 1.5mmol eight pure and mild 0.5ml octadecylenes of mercapto in another flask, this solution is heated to 150 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.To react the cation mono liquid solution and be heated to arbitrary temp between 180～240 ℃, 0.8mmol elemental sulfur (being dissolved in the 1.0ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes nanocrystal solution.Make CuIn
5S
8Quantum dot solution.
Embodiment 31:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot core and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Cu
11InS
7Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.1.1mmol cuprous chloride and 2.2mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 100 degree, until be down to 80 degree after the solution clarification.Add 0.1mmol indium acetate, the 0.5mmol eight pure and mild 0.5ml octadecylenes of mercapto in another flask, this solution is heated to 110 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～230 ℃, and 0.8mmol elemental sulfur (being dissolved in the 0.8ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes nanocrystal solution.Make Cu
11InS
7Quantum dot solution.
Embodiment 32:
Work as m=1, n=1, the synthetic quantum dot of typical case is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot core and III family is elementary composition can regulate arbitrarily its ratio:
Work as x: y＞1, one a typical quantum dot Cu
7InS
5Synthetic example is as follows:
At first the title complex for preparing copper, indium and mercapto alcohol.0.7mmol acetylacetone copper and 1.4mmol 18 mercapto alcohol are added in flask, add the 0.5ml octadecylene to be heated to 120 degree, until be down to 80 degree after the solution clarification.Add 0.1mmol indium acetate, the 0.3mmol eight pure and mild 0.5ml octadecylenes of mercapto in another flask, this solution is heated to 120 spends to rear cooling degree to 80 degree of solution clarification.The mercapto of copper and indium alcohol title complex is joined in reaction flask, adding 3ml octadecylene and 0.5mmol stearic acid.The cation mono liquid solution is heated to arbitrary temp between 150～240 ℃, and 0.6mmol elemental sulfur (being dissolved in the 0.6ml oleyl amine) injects rapidly reaction soln and kept 20 minutes, makes nanocrystal solution.Make Cu
7InS
5Quantum dot solution.
Second section: preparation I-III-VI/II-VI core-shell quanta dots (embodiment 33～35)
Embodiment 33:
Given here is that the synthetic I-III-VI quantum dot core of typical case of the present invention and ZnS are the quantum dot of shell.typical synthetic as follows: the I-III-VI quantum dot solution of embodiment 1～32 is arranged on 80 degree, the mixing solutions of 0.3mmol sulphur (0.3mmol sulphur is dissolved in the 1ml oleyl amine) and 0.3mmol zinc octadecanate (the 0.3mmol zinc octadecanate is dissolved in 0.5ml oleyl amine solution) is added in prepared I-III-VI quantum dot solution, solution is heated to 220 degree growing ZnS shells subsequently, after 30 minutes, solution is reduced to 100 degree, the mixing solutions of 0.4mmol sulphur (0.4mmol sulphur is dissolved in the 1ml oleyl amine) and 0.4mmol zinc octadecanate (the 0.4mmol zinc octadecanate is dissolved in 0.5ml oleyl amine solution) is joined in reaction soln, temperature is rising to 280 degree growing ZnS shells.Reaction experience is after 30 minutes, and solution is heated to 240 ° and kept 10 minutes.Finally, solution cool to room temperature.10ml ethanol and 1ml chloroform join in solution and centrifugation, and the quantum dot that obtains precipitation can be re-dispersed in normal hexane.
Embodiment 34:
Given here be the synthetic I-III-VI quantum dot core of typical case of the present invention and/ZnSe is the quantum dot of shell.typical synthetic as follows: embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 and 27 I-III-VI quantum dot solution is arranged on 90, 0.3mmol selenium (0.3mmol selenium urine is dissolved in the 1ml oleyl amine) and the mixing solutions of 0.3mmol zinc octadecanate (the 0.3mmol zinc octadecanate is dissolved in 0.5ml oleyl amine solution) are added in prepared I-III-VI quantum dot solution, solution is heated to 220 degree growing ZnSe shells subsequently, after 30 minutes, solution is reduced to 85 degree, 0.4mmol selenium (0.4mmol selenium urine is dissolved in the 1ml oleyl amine) and the mixing solutions of 0.4mmol zinc octadecanate (the 0.4mmol zinc octadecanate is dissolved in 0.5ml oleyl amine solution) are joined in reaction soln, temperature is being raised to 260 degree growing ZnSe shells.So repeat 4 circulations, the quantum dot solution cool to room temperature that obtains.10ml ethanol and 1ml chloroform join in solution and centrifugation, and the quantum dot that obtains precipitation can be re-dispersed in normal hexane.
Embodiment 35:
Given here is the quantum dot of the synthetic I-III-VI quantum dot core of typical case of the present invention and ZnSe/ZnSeS/ZnS composite shell.Typical synthetic as follows: embodiment 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26 and 27 I-III-VI quantum dot solution are arranged on 80 degree, the mixing solutions of 0.35mmol selenium (being dissolved in 1ml oleyl amine solution) and 0.3mmol zinc octadecanate (being dissolved in 0.5ml oleyl amine solution) is joined in prepared AgCuInGaSe quantum dot solution together, subsequently reaction is heated to 230 degree and increases the ZnSe shell.After 30 minutes, reaction soln is cooled to 100 degree, repeats above-mentioned growth ZnS shell experiment.After increasing the ZnSe layer of 2 molecular thickness, solution is down to 90 degree, 0.2mmol selenium urine (being dissolved in 0.5ml oleyl amine solution), 0.25mmol sulphur (being dissolved in 0.5ml oleyl amine solution) and 0.45mmol zinc octadecanate (being dissolved in 0.5ml oleyl amine solution) join in the reaction soln of above-mentioned preparation together, temperature is elevated to 30 minutes ZnSeS alloy shells of growing of 225 degree maintenances subsequently.Following reaction easily is reduced to 80 degree.Then 0.75mmol sulphur (being dissolved in 0.7ml oleyl amine solution) and 0.75mmol zinc octadecanate (being dissolved in 1ml oleyl amine solution) are joined simultaneously in reaction soln and gives birth to temperature to 240 degree.Increasing the ZnS shell after 30 minutes, solution is down to 100 and is spent and repeat to increase the ZnS shell, and the mixing solutions of 1mmol sulphur and 1mmol zinc octadecanate adds reaction soln to be heated to 260 to spend and keep 30 minutes growing ZnS shells.Finally reaction soln being heated to 280 spends and kept 5 minutes.Finally reaction soln is down to room temperature, adds the mixed solvent (volume ratio is 1: 10) of chloroform and ethanol to make the quantum dot precipitation, then centrifugation, be re-dispersed into the quantum dot particle that obtains in toluene.
Claims (3)
1. the preparation method of a nuclear shell structure quantum point, described nuclear shell structure quantum point, be with I
x-III
y-S
((x+3y)/2)For quantum dot core, Zn-VI are that the quantum dot shell forms; Wherein, I family element and III group element mol ratio are x/y, 1≤x≤11,1≤y≤11; I family element is copper or/and silver, and silver is 1-m/m with the copper mol ratio, 1 〉=m 〉=0, and the III group element is indium or/and gallium, and gallium and indium mol ratio are 1-n/n, 1 〉=n 〉=0, VI family element is sulphur or/and selenium, and selenium and sulphur mol ratio are 1-p/p, 1 〉=p 〉=0; The technological process that the coating of the preparation of quantum dot core solution and quantum dot shell is arranged;
The preparation process of described quantum dot core solution is take copper or/and silver-colored cationic monomer, indium or/and gallium cationic monomer, elemental sulfur are raw material, take octadecylene, octadecane or icosa alkene as solvent; Copper or/and silver-colored cationic monomer, indium or/and gallium cationic monomer, elemental sulfur feed intake by the quantum dot nuclear consitution; At first with copper or/and silver-colored cationic monomer and part 18 mercapto alcohol add in the first container, add solvent to be heated to solution clarification and be down to 75～85 ℃, obtain copper or/and the title complex of silver and part; Add indium or/and gallium cationic monomer, part eight mercapto alcohol and solvents are heated to the solution clarification in second container, cooling degree to 80 ℃ obtains indium or/and the title complex of gallium and part; Wherein the consumption of part be respectively copper by mol or/and silver-colored cationic monomer or indium or/and 2～5 times of gallium cationic monomer, solvent load by every mmol Cu or/and the cationic monomer of Ag uses 3～50mL; Finally with copper or/and silver and the title complex of part and indium or/and the title complex of gallium and part join in reaction vessel, be heated to 150～250 ℃, the oleyl amine solution that with concentration is the elemental sulfur of 0.8～2 mol/L injects reaction vessel and kept 20 minutes, makes quantum dot core solution;
The coating process of described quantum dot shell is take quantum dot core solution, sulphur or/and the cationic monomer of selenium anionic monomer, zinc as raw material, sulphur or/and the cationic monomer consumption of selenium anionic monomer and zinc feed intake by quantum dot shell component; Sulphur, or/and the cationic monomer of selenium anionic monomer, zinc is dissolved in respectively in oleyl amine, is joined after mixing in the quantum dot core solution of 80～100 ℃; Temperature of reaction is risen to 220～280 ℃ of growth quantum point shells 30～45 minutes; Be down to afterwards room temperature, adding volume ratio is that the mixed solvent of the chloroform of 1: 10 and ethanol makes the quantum dot precipitation, and then centrifugation is distributed to the quantum dot of the nucleocapsid structure that obtains in toluene or normal hexane.
2. the preparation method of nuclear shell structure quantum point according to claim 1, it is characterized in that, described copper is or/and silver-colored cationic monomer is neutralized verdigris, cuprous acetate, cupric nitrate, cuprous nitrate, cupric chloride, cuprous chloride, acetylacetone copper, Silver monoacetate or Silver Nitrate; Described indium is or/and the gallium cationic monomer is indium acetate, indium chloride, Indium Tris acetylacetonate, gallium chloride or methyl ethyl diketone gallium; The cationic monomer of described zinc is zinc acetate, zinc nitrate or zinc octadecanate; Described sulphur is or/and the selenium anionic monomer is elemental sulfur, simple substance selenium or selenium urine.
3. the preparation method of nuclear shell structure quantum point according to claim 1 and 2, is characterized in that, the coating process of described quantum dot shell repeats 2～3 times, forms 2～3 layers of Zn-VI quantum dot shell on quantum dot core; In adjacent quantum dot shell, be that ZnS, ZnSe or ZnSeS are alternate.
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