CN102212363A - Preparation method of core-shell structure quantum dot - Google Patents
Preparation method of core-shell structure quantum dot Download PDFInfo
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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 quantum dot by the nucleocapsid structure of regulation and control monomer reactivity and set of dispense is more controlled than preparation size, component is adjustable high fluorescence efficiency, physics and stable chemical performance.
Background technology
Near the electronic level of its fermi level is become discontinuous by original quasi-continuous state to back (1～20 nanometer) to a certain degree when the size of semiconductor crystal is little, and this phenomenon is called quantum size effect.Corresponding its character mainly depends on the crystalline size.Typical semiconductor nano is that quantum dot mainly comprises II-VI, III-V and IV-VI family.These quantum dots all show tangible 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 owing to the heavy metal that it does not contain severe toxicity is paid close attention to.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 current prepared go out the fluorescence efficiency of quantum dot generally be lower than 5%, and quantum dot instability.For example Castro reported in 2003 by the unimolecular reaction precursor method prepare that the quantum dot distribution of sizes that I-III-VI family quantum dot (Chem.Mater.2003,15,3142-3147)) obtains is relatively poor, fluorescence efficiency is less than 1%.Along with the synthetic development, reported I-III-VI family quantum dot by amine pyrolysis method (amine injects reaction monomers solution) preparation different structure (cube phase with six sides mutually) Lu group in 2008, these quantum dot size from 5 to 30 nanometers, there is not 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, by atomic shell continuous adsorption method (yin, yang ion alternation adding method) preparation nuclear shell structure quantum point, its efficient 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 C dSe 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 has only about 20%, 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, system need be finished under vacuum condition during the preparation quantum dot, quantum dot to some specific dimensions needs size Selection, these methods can be brought inconvenience, for example cost height, complicated operation for quantum dot is synthetic.And, consider that from the research aspect of material the composition of quantum dot and the research of property relationship yet there are no all reports, from this meaning, the controlled I-III-VI family quantum dot of component of preparation 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 control cationic activity, the way of injecting anionic monomer prepares I-III-VI family quantum dot.Form and temperature obtains controllable size, I-III-VI family quantum dot that component is adjustable first by the regulation and control monomer.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 is in the experiment of preparation shell, and utilization symbiosis regular way prepares 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 formed 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 utilization symbiosis regular way prepares 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 C dSe quantum dot fully, can satisfy field application demands such as biomarker, illumination and indicating meter substantially from the optical property aspect.
The quantum dot of the present invention's preparation is made up of I-III-VI family quantum dot nuclear and II-VI family quantum dot shell two portions.The material of forming these nanocrystal does not all contain the heavy metal element of severe toxicity.Concrete quantum dot nuclear 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 satisfy the valent requirement of molecule; That is, I family element is a copper or/and silver, and copper and silver-colored mol ratio are 1-m/m, 1 〉=m 〉=0; The III group element is an indium or/and gallium, and indium and gallium mol ratio are 1-n/n, 1 〉=n 〉=0; VI family element is a sulphur.Concrete quantum dot shell is Zn (S
pSe
1-p) promptly, II family element is a zinc, VI family element is a 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 nuclear by regulation and control cationic monomer activity, injection negatively charged ion precursor methods.Different cationic monomers forms title complex with different mercaptos alcohol, by adding the monomer of different ratios, injects anionic monomer at a certain temperature and can obtain I-III-VI family quantum dot nuclear.Prepare by the symbiosis regular way for the quantum dot shell.The symbiosis regular way is exactly the method that the material of growth shell is mixed together adding growth quantum point shell.The mix monomer of shell material injects in low temperature, postheating solution prepares shell to higher temperature, symbiosis length once is the thickness B1 layer as shown in Figure 1 of an individual molecule layer material, adds the repetitive operation of differing materials monomer again and can prepare B2 layer and B3 layer respectively.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 mainly is that S and Zn are alternately added, and not have to add the part that is fit to, and as mercapto alcohol etc., and reacts and must carry 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 is with I
x-III
y-S
((x+3y)/2)For quantum dot nuclear, Zn-VI constitute for the quantum dot shell; Wherein, I family element and III group element mol ratio are x/y, 1≤x≤11,1≤y≤11; I family element is a copper or/and silver, and silver is 1-m/m with the copper mol ratio, 1 〉=m 〉=0, and the III group element is an indium or/and gallium, and gallium and indium mol ratio are 1-n/n, 1 〉=n 〉=0, VI family element is a 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 nuclear solution and quantum dot shell is arranged;
The preparation process of described quantum dot nuclear solution is with copper or/and silver-colored cationic monomer, indium or/and gallium cationic monomer, elemental sulfur are raw material, or/and long chain acid is a part, are solvent with octadecylene, octadecane or icosa alkene with mercapto alcohol; 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 first container, add solvent and be heated to the solution clarification and reduce 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 not copper by mole score 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; At last with copper or/and silver and the title complex of part and indium or/and the title complex of gallium and part join in the reaction vessel, be heated to 150～250 ℃, be that the oleyl amine solution of the elemental sulfur of 0.8～2 mol injects reaction vessel and kept 20 minutes with concentration, make quantum dot nuclear solution;
The coating process of described quantum dot shell, be with quantum dot nuclear solution, sulphur or/and the cationic monomer of selenium anionic monomer, zinc is a raw material, sulphur or/and the cationic monomer consumption of selenium anionic monomer and zinc feed intake by quantum dot shell component; Or/and the cationic monomer of selenium anionic monomer, zinc is dissolved in respectively in the oleyl amine, the quantum dot that joins 80～100 ℃ after the mixing is examined in the solution with sulphur; Temperature of reaction is risen to 220～280 ℃ of growth quantum point shells 30～45 minutes; Reduce to room temperature afterwards, the chloroform and the ethanol mixed solvent that added volume ratio and be 1: 10 make the quantum dot precipitation, and centrifugation then is distributed to the quantum dot of the nucleocapsid structure that obtains in toluene or the normal hexane.
The nuclear shell structure quantum point of the inventive method preparation has satisfactory stability and higher quantum yield.Chemical stability is after at room temperature placing 6 months, the fluorescence efficiency no change.For the quantum dot nuclear of preparation, its efficient is below 5%.The measurement of quantum yield is to calculate by the contrast rhodamine 6G to obtain, and laboratory sample is by the integrating sphere test shows, and the error of efficient is no more than 5%.The quantum dot efficient at least 25% of the present invention preparation is optimized the quantum dot efficient at least 40% of the composition of nuclear, further optimizes quantum dot efficient that the shell material obtains at least more than 60%.Comprise the intermediary value equally for its efficient of prepared quantum dot.
The quantum dot nuclear of the present invention's preparation, shell surface ligand 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 nuclear 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 the 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 of/ZnS nucleocapsid structure and emmission spectrum.
The quantum dot of the inventive method preparation need be regulated and control the cationic monomer activity.The title complex that needs 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.The required material of preparation quantum dot comprises copper, indium, silver, gallium, zinc.Anionic monomer has sulphur and selenium, before the injection anionic monomer it is dissolved in oleyl amine.
In preparation different part and monomeric complex compound, add an amount of lipid acid and further 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 only is 3 nanometers.Long chain acid mainly contains stearic acid, TETRADECONIC ACID and eight acid etc.
The present invention is that the oil phase legal system is equipped with quantum dot nuclear and quantum dot shell, and the solvent of reaction usefulness is non-corrdination type solvent, for example octadecylene, octadecane, icosa alkene etc.Because the quantum dot surface is chain alkyl amine, acid and/or mercapto alcohol, an amount of acetone or ethanol add and cause the quantum dot precipitation, and then are distributed to again in organic solvent such as toluene or the normal hexane equal solvent.In the process of purifying, quantum dot keeps original physics and chemical property, and efficient 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 is regulated and control 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 synoptic 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 of/ZnS nuclear shell structure quantum point and emmission spectrum figure.
Fig. 3 is the CuIn that the present invention prepares
3S
5The transmission electron microscope photo of/ZnS nuclear shell structure quantum point.
Embodiment:
First part: preparation I-III-VI family's quantum dot nuclear (embodiment 1～32)
The present invention of being given here has different components I
x-III
y-S
((x+3y)/2)Quantum dot nuclear, x wherein, y be greater than zero any number promptly: 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 is formed 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. promptly: 1 〉=m 〉=0,1 〉=n 〉=0.The molar ratio that method notable feature of the present invention is exactly a particle is in full accord with the composition that makes particle.
Embodiment 1:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Cu
4In
2S
5Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercaptos alcohol are added in the flask, add and reduce to 80 degree after the 0.5ml octadecylene is heated to the solution clarification.Add the 0.2mmol indium acetate in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
4In
2S
5Quantum dot solution.
Embodiment 2:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot Cu
2In
4S
7Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.0.2mmol neutralized verdigris and 0.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol indium acetate, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
2In
4S
7Quantum dot solution.
Embodiment 3:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y=1, a typical quantum dot CuInS
2Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol indium acetate, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes CuInS
2Quantum dot solution.
It is the CuInS of preparation different size that reaction soln is heated to
2Quantum dot.
Embodiment 4:
Work as m=1, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Cu
4InGaS
5Synthetic example is as follows:
The title complex that at first prepares copper, indium, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add 0.1mmol indium acetate, 0.1mmol acetic acid gallium in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to solution clarification back cooling degree to 80 degree with this solution.The mercapto alcohol title complex of copper, gallium and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
4InGaS
5Quantum dot solution.
Embodiment 5:
Work as m=1, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot Cu
2In
2Ga
2S
7Synthetic example is as follows:
The title complex that at first prepares copper, indium, gallium and mercapto alcohol.0.2mmol neutralized verdigris and 0.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.2mmol indium acetate, 0.2mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper, gallium and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
2In
2Ga
2S
7Quantum dot solution.
Embodiment 6:
Work as m=1, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y=1, a typical quantum dot Cu
2InGaS
4Synthetic example is as follows:
The title complex that at first prepares copper, indium, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol indium acetate, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 120 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper, gallium and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
2InGaS
4Quantum dot solution.
Embodiment 7:
Work as m=1, n=0, typical synthetic quantum dot is Cu
xGa
yS
((x+3y)/2), wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Cu
4Ga
2S
5Synthetic example is as follows:
The title complex that at first prepares copper, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add 0.2mmol acetic acid gallium in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
4Ga
2S
5Quantum dot solution.
Embodiment 8:
Work as m=1, n=0, typical synthetic quantum dot is Cu
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot Cu
2Ga
4S
7Synthetic example is as follows:
The title complex that at first prepares copper, gallium and mercapto alcohol.0.2mmol neutralized verdigris and 0.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
2Ga
4S
7Quantum dot solution.
Embodiment 9:
Work as m=1, n=0, typical synthetic quantum dot is Cu
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y=1, a typical quantum dot CuGaS
2Synthetic example is as follows:
The title complex that at first prepares copper, gallium and mercapto alcohol.0.4mmol neutralized verdigris and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes CuGaS
2Quantum dot solution.
Embodiment 10:
Work as m=0.5, n=1, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Ag
2Cu
2In
2S
5Synthetic example is as follows:
The title complex that at first prepares silver, copper, indium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add the 0.2mmol indium acetate in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Ag
2Cu
2In
2S
5Quantum dot solution.
Embodiment 11:
Work as m=0.5, n=1, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot AgCuIn
4S
7Synthetic example is as follows:
The title complex that at first prepares silver, copper, indium and mercapto alcohol.0.1mmol Silver monoacetate, 0.1mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add the 0.4mmol indium acetate in another flask, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes AgCuIn
4S
7Quantum dot solution.
Embodiment 12:
Work as m=0.5, n=1, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y=1, a typical quantum dot AgCuGa
2S
4Synthetic example is as follows:
The title complex that at first prepares silver, copper, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes CuGaS
2Quantum dot solution.
Embodiment 13
Work as m=0.5, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Ag
2Cu
2InGaS
5Synthetic example is as follows:
The title complex that at first prepares silver, copper, indium, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.1mmol indium acetate, the pure and mild 0.8ml octadecylene of 0.1mmol acetic acid gallium 0.6mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper, indium and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Ag
2Cu
2InGaS
5Quantum dot solution.
Embodiment 14
Work as m=0.5, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot AgCuIn
2Ga
2S
7Synthetic example is as follows:
The title complex that at first prepares silver, copper, indium, gallium and mercapto alcohol.0.1mmol Silver monoacetate, 0.1mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.2mmol indium acetate, 0.2mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper, indium and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes AgCuIn
2Ga
2S
7Quantum dot solution.
Embodiment 15:
Work as m=0.5, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y=1, a typical quantum dot AgCuGaInS
4Synthetic example is as follows:
The title complex that at first prepares silver, copper, indium, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.2mmol acetic acid gallium, 0.2mmol indium acetate, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper, indium and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes AgCuGaInS
4Quantum dot solution.
Embodiment 16:
Work as m=0.5, n=0, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Cu
2Ag
2Ga
2S
5Synthetic example is as follows:
The title complex that at first prepares copper, indium gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add 0.2mmol acetic acid gallium in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Cu
2Ag
2Ga
2S
5Quantum dot solution.
Embodiment 17:
Work as m=0.5, n=0, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot CuAgGa
4S
7Synthetic example is as follows:
The title complex that at first prepares copper, silver-colored gallium and mercapto alcohol.0.1mmol Silver monoacetate, 0.1mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes CuAgGa
4S
7Quantum dot solution.
Embodiment 18:
Work as m=0.5, n=0, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y=1, a typical quantum dot AgCuGa
2S
4Synthetic example is as follows:
The title complex that at first prepares silver, copper, gallium and mercapto alcohol.0.2mmol Silver monoacetate, 0.2mmol neutralized verdigris and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, copper and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes AgCuGa
2S
4Quantum dot solution.
Embodiment 19:
Work as m=0, n=1, typical synthetic quantum dot is Ag
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Ag
4In
2S
5Synthetic example is as follows:
The title complex that at first prepares silver, indium and mercapto alcohol.0.4mmol Silver monoacetate and 0.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add the 0.2mmol indium acetate in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Ag
4In
2S
5Quantum dot solution.
Embodiment 20:
Work as m=0, n=1, typical synthetic quantum dot is Ag
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot Ag
2In
4S
7Synthetic example is as follows:
The title complex that at first prepares silver, indium and mercapto alcohol.0.2mmol Silver monoacetate and 0.2mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol indium acetate, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Ag
2In
4S
7Quantum dot solution.
Embodiment 21:
Work as m=0, n=1, typical synthetic quantum dot is Ag
xIn
yS
((x+3y)/2), wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y=1, a typical quantum dot AgInS
2Synthetic example is as follows:
The title complex that at first prepares silver, indium and mercapto alcohol.0.4mmol Silver monoacetate and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol indium acetate, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes AgInS
2Quantum dot solution.
Embodiment 22:
Work as m=0, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Ag
4InGaS
5Synthetic example is as follows:
The title complex that at first prepares silver, indium, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add 0.1mmol indium acetate, 0.1mmol acetic acid gallium in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, gallium and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Ag
4InGaS
5Quantum dot solution.
Embodiment 23:
Work as m=0, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot Ag
2In
2Ga
2S
7Synthetic example is as follows:
The title complex that at first prepares silver, indium, gallium and mercapto alcohol.0.2mmol Silver monoacetate and 0.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.2mmol indium acetate, 0.2mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, gallium and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Ag
2In
2Ga
2S
7Quantum dot solution.
Embodiment 24:
Work as m=0, n=0.5, typical synthetic quantum dot 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 its ratio arbitrarily:
Work as x: y=1, a typical quantum dot Ag
2InGaS
4Synthetic example is as follows:
The title complex that at first prepares silver, indium, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol indium acetate, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver, gallium and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes Ag
2InGaS
4Quantum dot solution.
Embodiment 25:
Work as m=0, n=0, typical synthetic quantum dot is Ag
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Ag
4Ga
2S
5Synthetic example is as follows:
The title complex that at first prepares silver, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.Add 0.2mmol acetic acid gallium in another flask, the pure and mild 0.8ml octadecylene of 0.6mmol eight mercaptos is heated to 150 with this solution and spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes.Make Ag
4Ga
2S
5Quantum dot solution.
Embodiment 26:
Work as m=0, n=0, typical synthetic quantum dot is Ag
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot Ag
2Ga
4S
7Synthetic example is as follows:
The title complex that at first prepares silver, gallium and mercapto alcohol.0.2mmol Silver monoacetate and 0.2mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of silver and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes.Make Ag
2Ga
4S
7Quantum dot solution.
Embodiment 27:
Work as m=0, n=0, typical synthetic quantum dot is Ag
xGa
yS
((x+3y)/2): wherein form the I family element of quantum dot and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y=1, a typical quantum dot AgGaS
2Synthetic example is as follows:
The title complex that at first prepares silver, gallium and mercapto alcohol.0.4mmol Silver monoacetate and 0.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.4mmol acetic acid gallium, the pure and mild 0.8ml octadecylene of 1.2mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper silver and gallium is joined in the 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 reaction soln rapidly and kept 20 minutes.Make AgGaS
2Quantum dot solution
Embodiment 28:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot nuclear and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot CuIn
11S
17Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.0.1mmol cupric chloride and 0.8mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 140 degree, after the solution clarification, reduce to 80 degree.In another flask, add 1.1mmol indium acetate, the pure and mild 0.7ml octadecylene of 3.3mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes nanocrystal solution.Make CuIn
11S
17Quantum dot solution.
Embodiment 29:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot nuclear and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot CuIn
7S
11Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.0.1mmol cupric nitrate and 0.6mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 130 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.7mmol indium acetate, the pure and mild 0.9ml octadecylene of 2.1mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes nanocrystal solution.Make CuIn
7S
11Quantum dot solution.
Embodiment 30:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot nuclear and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＜1, one a typical quantum dot CuIn
5S
8Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.0.1mmol cuprous acetate and 0.2mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 130 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.5mmol indium acetate, the pure and mild 0.5ml octadecylene of 1.5mmol eight mercaptos, this solution is heated to 150 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes nanocrystal solution.Make CuIn
5S
8Quantum dot solution.
Embodiment 31:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot nuclear and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Cu
11InS
7Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.1.1mmol cuprous chloride and 2.2mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 100 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.1mmol indium acetate, the pure and mild 0.5ml octadecylene of 0.5mmol eight mercaptos, this solution is heated to 110 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly and kept 20 minutes, makes nanocrystal solution.Make Cu
11InS
7Quantum dot solution.
Embodiment 32:
Work as m=1, n=1, typical synthetic quantum dot is Cu
xIn
yS
((x+3y)/2): wherein form the I family element of quantum dot nuclear and III family is elementary composition can regulate its ratio arbitrarily:
Work as x: y＞1, one a typical quantum dot Cu
7InS
5Synthetic example is as follows:
The title complex that at first prepares copper, indium and mercapto alcohol.0.7mmol acetylacetone copper and 1.4mmol 18 mercaptos alcohol are added in the flask, add the 0.5ml octadecylene and be heated to 120 degree, after the solution clarification, reduce to 80 degree.In another flask, add 0.1mmol indium acetate, the pure and mild 0.5ml octadecylene of 0.3mmol eight mercaptos, this solution is heated to 120 spends to solution clarification back cooling degree to 80 degree.The mercapto alcohol title complex of copper and indium is joined in the 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 reaction soln rapidly 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 synthetic I-III-VI quantum dot nuclear 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 the 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 the reaction soln, and 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 the solution and centrifugation, and the quantum dot that obtains precipitation can be distributed in the normal hexane again.
Embodiment 34:
Given here be the synthetic I-III-VI quantum dot nuclear 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, the mixing solutions of 0.3mmol selenium (0.3mmol selenium urine 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 the 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, the 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 the reaction soln, and 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 the solution and centrifugation, and the quantum dot that obtains precipitation can be distributed in the normal hexane again.
Embodiment 35:
Given here is the quantum dot of synthetic I-III-VI quantum dot nuclear 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 the 1ml oleyl amine solution) and 0.3mmol zinc octadecanate (being dissolved in 0.5ml oleyl amine solution) is joined in the 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 reduced 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 the 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.Be reduced to 80 degree easily with afterreaction.Join in the reaction soln 0.75mmol sulphur (being dissolved in the 0.7ml oleyl amine solution) and 0.75mmol zinc octadecanate (being dissolved in 1ml oleyl amine solution) also living warm simultaneously then to 240 degree.Increasing the ZnS shell after 30 minutes, solution is reduced to 100 degree and is repeated to increase the ZnS shell, and the mixing solutions of 1mmol sulphur and 1mmol zinc octadecanate adds reaction soln and is heated to 260 degree and keeps 30 minutes growing ZnS shells.At last reaction soln is heated to 280 the degree and kept 5 minutes.At last reaction soln is reduced to room temperature, add chloroform and ethanol mixed solvent (volume ratio is 1: 10) and make the quantum dot precipitation, centrifugation then is distributed to the quantum dot particle that obtains in the toluene again.
Claims (4)
1. the preparation method of a nuclear shell structure quantum point, described nuclear shell structure quantum point is with I
x-III
y-S
((x+3y)/2)For quantum dot nuclear, Zn-VI constitute for the quantum dot shell; Wherein, I family element and III group element mol ratio are x/y, 1≤x≤11,1≤y≤11; I family element is a copper or/and silver, and silver is 1-m/m with the copper mol ratio, 1 〉=m 〉=0, and the III group element is an indium or/and gallium, and gallium and indium mol ratio are 1-n/n, 1 〉=n 〉=0, VI family element is a 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 nuclear solution and quantum dot shell is arranged;
The preparation process of described quantum dot nuclear solution is with copper or/and silver-colored cationic monomer, indium or/and gallium cationic monomer, elemental sulfur are raw material, or/and long chain acid is a part, are solvent with octadecylene, octadecane or icosa alkene with mercapto alcohol; 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 first container, add solvent and be heated to the solution clarification and reduce 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 not copper by mole score 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; At last with copper or/and silver and the title complex of part and indium or/and the title complex of gallium and part join in the reaction vessel, be heated to 150～250 ℃, be that the oleyl amine solution of the elemental sulfur of 0.8～2 mol injects reaction vessel and kept 20 minutes with concentration, make quantum dot nuclear solution;
The coating process of described quantum dot shell, be with quantum dot nuclear solution, sulphur or/and the cationic monomer of selenium anionic monomer, zinc is a raw material, sulphur or/and the cationic monomer consumption of selenium anionic monomer and zinc feed intake by quantum dot shell component; Or/and the cationic monomer of selenium anionic monomer, zinc is dissolved in respectively in the oleyl amine, the quantum dot that joins 80～100 ℃ after the mixing is examined in the solution with sulphur; Temperature of reaction is risen to 220～280 ℃ of growth quantum point shells 30～45 minutes; Reduce to room temperature afterwards, the chloroform and the ethanol mixed solvent that added volume ratio and be 1: 10 make the quantum dot precipitation, and centrifugation then is distributed to the quantum dot of the nucleocapsid structure that obtains in toluene or the 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; Described mercapto alcohol is dodecyl mercapto alcohol, eight alkyl mercapto alcohol or octadecyl mercapto alcohol.
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 nanocrystalline shell repeats 2～3 times, forms 2～3 layers of nanocrystalline shell of Zn-VI on nanocrystal; In the adjacent nanocrystalline shell, VI family element is that ZnS, ZnSe or ZnSeS are alternate.
4. the preparation method of nuclear shell structure quantum point according to claim 1 and 2, it is characterized in that, the preparation process of described nanocrystal solution, copper is or/and the mercapto alcohol in the title complex of silver and mercapto alcohol is 18 mercapto alcohol, indium is or/and the mercapto alcohol in the title complex of gallium and mercapto alcohol is eight mercapto alcohol.
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