CN102660288A - Method for preparing chalcopyrite structure CuInSe2 or/and CuInSe2/ZnS core-shell structure quantum dots - Google Patents
Method for preparing chalcopyrite structure CuInSe2 or/and CuInSe2/ZnS core-shell structure quantum dots Download PDFInfo
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Abstract
The invention relates to a method for preparing chalcopyrite structure CuInSe2 or/and CuInSe2/ZnS core-shell structure quantum dots, comprising the following steps: firstly preparing an In3<+>, Cu<+> cation precursor solution, rapidly heating up from room temperature to 200-250 DEG C under the protection of argon, rapidly injecting an Se precursor solution, reacting for 15-60 min to obtain a CuInSe2 quantum dot solution; reacting for 30-60min at 190-230 DEG C by dropwisely adding a zinc precursor solution, then naturally cooling to room temperature, and carrying out centrifugal purification to obtain CuInSe2/ZnS core-shell structure quantum dots, wherein the obtained CuInSe2 quantum dots have a chalcopyrite crystal structure, the atomic ratio of Cu to In to Se is close to 1 to 1 to 2, the range of the fluorescence emission peak of the CuInSe2/ZnS core-shell structure quantum dots is 700-960 nm, and the fluorescence quantum yield is 19.8-33.4 %. According to the invention, the method uses the low-cost Se precursor, the process is simple, the synthetic period is short, the method is beneficial for batch production, and the synthesized CuInSe2/ZnS quantum dots are near-infrared luminous and have good fluorescence efficiency, and lay the foundations for the application of quantum dots in bioluminescence imaging in vivo.
Description
Technical field
The present invention relates to compound semiconductor nano material preparation technical field, particularly a kind of yellow copper structure CuInSe
2And CuInSe
2The preparation method of the quantum dot of/ZnS nucleocapsid structure.
Background technology
Quantum dot (QDs) is the nano material of accurate zero dimension, constitute by a spot of atom, its particulate physical diameter in the 1-10nm scope, less than or near the exciton Bohr radius.Based on quantum effect, quantum dot has unique optical property, is that a kind of inorganic semiconductor light emitting is nanocrystalline.Compare with traditional organic fluorescence element, quantum dot has exciting light spectrum width and continuous distribution, the narrow and gaussian symmetric of emission peak, nothing hangover, advantage such as Stokes shift is big, and photochemical stability is strong, and fluorescence lifetime is long.In addition, the quantum dot of process chemically modified has excellent biological compatibility, and structure and properties is more stable; And can carry out the specificity connection; Cytotoxicity is low, and is little to organism harm, therefore at detection ranges such as cell imaging, molecular imprinting, living microbe marks wide development space arranged.
The research of quantum dot at present mainly concentrates on II-VI family (like ZnS, CdSe), III-V family (like InP, InAs and GaAs) and I-III-VI family (like Cu-In-Se and Cu-In-S) quantum dot.Although the research of II-VI family element quantum dot reaches its maturity; And fields such as biomedical imaging, life science and fluorescent device have extensively been applied to; But because heavy metal element toxicity such as its Cd, Hg and Pb and transmitted wave length are prone to by factors such as biological tissue's scattering absorptions; Can not be used for in-vivo diagnostic, limit its application aspect the living body biological medical imaging.Emission wavelength then receives biological tissue scattering and inhalation effects less near infrared (NIR) quantum dot of 700-900nm, has the favorable tissue penetrativity and can overcome the influence of the autofluorescence of biological tissue effectively, helps medical imaging in the body.Wherein III-V family and I-III-VI group element compound are because the energy gap of its material own is less; Present researchist has prepared the fluorescent emission wavelength and has been positioned at near-infrared region (650～1100nm) quantum dot; Like InP/ZnS, CuInSe and CuInS quantum dot, for later application at the living microbe diagnostic field provides possibility.Because the needed reacting precursor of preparation III-V group element compound is like three (trimethyl silicane) phosphorus (P (TMS)
3), expensive and poor chemical stability, required experiment condition harshness is unfavorable for mass production, so the I-III-VI group element compound becomes the first-selection of research.Wherein the energy gap of Cu-In-Se semiconductor material own is less, the near infrared band gap is luminous, and heavy metal free toxicity, thereby becomes the focus of Recent study gradually.
Although synthetic and application facet is reported to some extent at Cu-In-Se at present, also just rest on the desk study stage.Because there is great difference in the reactive behavior of Cu+ and In3+; Two kinds of direct reactive behavioies of positively charged ion of active balance how; Select suitable part, the synthetic uniform particle diameter of control, composition is identical and quantum dot with high fluorescence efficiency becomes the research difficult point in this field.In in recent years, the Cu-In-Se of some bibliographical informations have been arranged solution synthetic yellow copper structure and zincblende lattce structure is nanocrystalline.Because the quantum yield that obtains is generally lower, in order further to improve the quantum yield of Cu-In-Se quantum dot, strengthen its photochemical stability, more common method is at the inorganic shell of Cu-In-Se quantum dot surface growth ZnS at present.Nose etc. have synthesized the CuInSe of emission wavelength in the 820-940nm scope
2Quantum dot, but fluorescence quantum yield less than 5%; And Cassette etc. have studied with selenourea as the synthetic CuInSe of one pot of thermal decomposition method of selenium presoma
2And CuInSe
2/ ZnS nuclear/shell quantum dot, emission wavelength be in the 700-1000nm scope, and fluorescent emission is that the quantum yield of the quantum dot of 800nm is brought up to 40-50% behind the ZnS involucrum.Though the fluorescent yield of quantum dot has improved, because its expensive cost of material makes the application of quantum dot be restricted.
On the technical foundation of existing public reported, to the quantum dot synthetic was not enough in the past, we have carried out some technological improvements, low, the good stability of not only selecting for use of precursor raw material price, and the CuInSe that obtains
2And CuInSe
2/ ZnS quantum dot fluorescence intensity is good, and quantum yield is high, and preparation technology is also simpler, and is repeatable strong, for the application of diagnosing at living microbe later on lays the foundation.
Summary of the invention
The objective of the invention is to propose a kind of CuInSe of high fluorescence quality
2And CuInSe
2The preparation method of/ZnS nuclear shell structure quantum point further simplifies and improves present CuInSe
2, CuInSe
2The preparation technology of/ZnS nuclear shell structure quantum point.
Technical scheme of the present invention is following:
A kind of yellow copper structure CuInSe
2The preparation method of quantum dot is characterized in that step is following:
1) preparation contains Cu
+, In
3+Cation precursor solution and Se precursor solution;
2) under argon shield, cation precursor quickly heated up to 200～250 ℃ after, inject the Se precursor solution rapidly, remove thermal source behind reaction 15～60min and naturally cool to room temperature;
3) centrifugal purification promptly obtains the CuInSe of yellow copper structure
2Quantum dot.
Described step 1) is with indium acetate (In (Ac)
3), indium chloride (InCl
3) or indium iodide (InI
3) be the indium source; With cuprous acetate (CuAc), cuprous chloride (CuCl) or cuprous iodide (CuI) is the copper source; With backbone length is that the saturated fatty mercaptan of 8～18 carbon atoms is as part and activity inhibitor; With octadecylene as reaction solvent, the Cu of the clear that under the condition of protection of inert gas, obtains through magnetic agitation 30min
+, In
3+Cation precursor solution.
Cu in the described step 1) cation precursor solution
+, In
3+Mol ratio is 1: 1～1: 3, Cu
+, In
3+Cationic and with the mol ratio of part be 1: 10～1: 40.
Described step 1) Se precursor solution is to be the Se source with Se simple substance, is part with three normal-butyl phosphorus or three n-octyl phosphorus, and the mol ratio of Se and part is 1: 3, and is that solvent supersonic dissolves body fluid before the Se of the 0.2M that obtains clear with the octadecylene.The Se precursor and the Cu that add in said second step
+, In
3+Cationic and molar ratio is 2: 1.
A kind of yellow copper structure CuInSe
2/ ZnS nuclear shell structure quantum point preparation method is characterized in that: at preparation CuInSe
2The step 2 of quantum dot); After injecting Se precursor solution reaction 15～60min, temperature of reaction is transferred to 190～230 ℃, dropwise drip the zinc precursor solution; React and remove thermal source behind the 30-60min and naturally cool to room temperature, centrifugal purification obtains yellow copper structure CuInSe2/ZnS nuclear shell structure quantum point.
Described zinc precursor solution is with Zinic stearas (Zn (SA)
2) or zinc acetate (Zn (Ac)
2) be the zinc source, oleic acid or oleyl amine are part, and the mol ratio of zinc source and part is 1: 6, are body fluid before the zinc of the 0.1M for preparing of solvent heating with the octadecylene.
The yellow copper structure CuInSe that the present invention obtains
2Quantum dot carries out X-ray diffraction (XRD) and electron spectroscopy analysis (EDX).Can find out made CuInSe from the XRD figure spectrum of accompanying drawing 1
2The XRD figure spectrum of quantum dot goes up and has three primary structure characteristic peaks, and promptly 26.70 °, 44.01 ° and 52.23 °, correspond respectively to (112) in the yellow copper ore crystalline structure, (204)/(220) and (116)/(312) prove the CuInSe by the present technique preparation
2Quantum dot has the yellow copper ore crystalline structure.Can draw CuInSe from the EDX collection of illustrative plates of accompanying drawing 2
2The atomic ratio of Cu in the quantum dot: In: Se is formed stable and is met stoichiometric ratio all about 1: 1: 2.
The yellow copper structure CuInSe that the present invention obtains
2Scope 700～the 960nm of the fluorescent emission peak position of/ZnS core-shell quanta dots, fluorescence quantum yield are 19.8～33.4%.
In the step 1) of the present invention, Cu
+, In
3+Cation precursor liquid in copper source and indium source mol ratio be 1: 1～1: 3, Cu
+, In
3+Cationic and with the part mol ratio be 1: 10～1: 40.Octadecylene is as this dissolvant of reaction system, do not have remarkable influence for the performance of products made thereby, so there is not strict quantitative limitation, selects about 6-8ml.The saturated fatty mercaptan of 8～18 carbon atoms is as the part solvent of whole reaction system, because itself and In
3+, Cu
+Have good coordination, can be used as a kind of effective part and prepare In, Cu precursor solution, and can effectively prevent nanocrystalline reunion under hot conditions.In this step, remove oxygen and moisture in the system through the means that vacuumize, avoid In
3+And Cu
+Hydrolysis under hot conditions.
In the step 1) of the present invention before the Se in the body fluid mol ratio of Se and part be 1: 3 because TBP and TOP have coordination, so effectively coordination and be the solution of 0.2M in the solvent octadecylene through the concentration that ultrasonic dissolution obtains clear; Se precursor and Cu
+, In
3+Cationic and molar ratio is 2: 1, and the atomic ratio that helps better controlled Cu: In: Se generates and forms the CuInSe that stablizes and meet stoichiometric ratio about 1: 1: 2
2Quantum dot.
Zinc source and part mol ratio are 1: 6 in the zinc precursor solution of the present invention, and zinc source and part can prepare the even zinc precursor solution of 0.1M through heating in octadecylene.CuInSe
2Quantum dot is through involucrum, and fluorescence quantum yield is 19.8～33.4%, and photochemical stability and quantum yield effectively improve.
The present invention obtains CuInSe through centrifugal purification at last
2/ ZnS nuclear shell structure quantum point, and calculate fluorescence quantum efficiency, adopt method of calculation following:
The present invention adopts dilute solution fluorescence reference installation to made CuInSe
2, CuInSe
2The fluorescence quantum yield of/ZnS nuclear shell structure quantum point carries out quantification; This method uses spectrophotofluorometer and ultraviolet-visible spectrophotometer to be testing tool, and concrete measuring process is: the absorbancy under certain wavelength selected of fluorescent substance to be measured and reference material is measured in (1); (2) under wavelength selected,, record the fluorescence emission spectrum of determinand and reference material respectively with same shooting conditions; (3) quantum yield through the computes test substance:
In the following formula
With
The quantum yield of representing testing sample and reference material respectively, F and F
sThe integral area of representing the emission spectrum of testing sample and reference material respectively, A and A
sRepresent testing sample and the reference material absorbancy under corresponding exciting light respectively, n and n
sThe specific refractory power of representing testing sample and reference material solvent for use respectively.The quantum yield 0.95 that the present invention records with the 470nm optical excitation in ethanolic soln with rhodamine 6G is reference (reference material solution is being prepared later 12h with interior use), has measured CuInSe
2The fluorescence quantum yield of/ZnS nuclear shell structure quantum point.
1), the precursor raw material of the costliness avoided uses the present invention compares prior art, and biggest advantage and difference are:, cost economizes in raw materials; 2), adopt simple hot injection, easy and simple to handle, safety is prone to row, has simplified present preparation technology, and is repeatable strong; 3), synthetic CuInSe of the present invention
2The fluorescence quantum yield 19.8-33.4% of/ZnS quantum dot, fluorescent emission scope 700～960nm can satisfy the requirement of bio-medical diagnosis; 4), synthesis cycle of the present invention is short, technology is simple, is beneficial to mass production.
Description of drawings
The CuInSe that Fig. 1: embodiment 1,2,3 is made
2The X-ray diffraction of nuclear shell structure quantum point (XRD) collection of illustrative plates;
The CuInSe that Fig. 2: embodiment 1,2,3 is made
2Electron energy analysis (EDX) collection of illustrative plates of nuclear shell structure quantum point;
The CuInSe that Fig. 3: embodiment 4 is made
2The fluorescent emission of/ZnS nuclear shell structure quantum point and uv absorption spectrum synoptic diagram;
The CuInSe that Fig. 4: embodiment 5 is made
2The fluorescent emission of/ZnS nuclear shell structure quantum point and uv absorption spectrum synoptic diagram;
The CuInSe that Fig. 5: embodiment 6 is made
2The fluorescent emission of/ZnS nuclear shell structure quantum point and uv absorption spectrum synoptic diagram.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are made detailed description: present embodiment is being to implement under the prerequisite with technical scheme of the present invention, and given detailed embodiment and process are to further specify of the present invention, rather than limit scope of the present invention.
Implementation process step of the present invention is following:
1) preparation contains Cu
+, In
3+Cation precursor solution, Se precursor solution and zinc before body fluid;
2) under argon shield, the Cu that step 1) is obtained
+, In
3+Cation precursor liquid quickly heats up to 200～250 ℃,, inject the Se precursor solution, remove thermal source behind reaction 15～60min and naturally cool to room temperature; Centrifugal purification promptly obtains the CuInSe of yellow copper structure
2Quantum dot.If preparation CuInSe
2/ ZnS nuclear shell structure quantum point does not then cool off the centrifugal purification operation in this step, directly carry out next step reaction.
3) with reaction solution behind 200～250 ℃ of reacting by heating 15～60min, temperature of reaction is transferred to 190～230 ℃, dropwise drip the zinc precursor solution, react again and remove thermal source behind the 30-60min and naturally cool to room temperature, centrifugal purification obtains yellow copper structure CuInSe
2/ ZnS nuclear shell structure quantum point.
Embodiment 1:
1) takes by weighing 29.2mg (0.1mmol) In (Ac)
3, 9.9mg (0.1mmol) CuCl and adds 1.39ml (8mmol) octyl mercaptan in a 25ml four-hole boiling flask, and the octadecylene of 6ml stirs 30min vacuumizing the condition lower magnetic force, is dissolved to clarification fully to positively charged ion precursor liquid, obtains Cu
+, In
3+Cation precursor solution; Take by weighing 31.6mg (0.4mmol) simple substance Se, in a single port round-bottomed bottle, and add the octadecylene of 536ul (1.2mmol) TOP, 2ml, excusing from death is dissolved to clarification and obtains body fluid before the Se.
2) in system, recharge argon gas, with Cu
+, In
3+Cation precursor solution is rapidly heated from room temperature and is heated to 230 ℃, injects the Se precursor solution, removes thermal source behind the reaction 45min and is cooled to room temperature, and centrifugal purification obtains CuInSe
2Quantum dot;
As shown in Figure 1, the CuInSe of acquisition
2The XRD figure of quantum dot spectrum proved resulting nanocrystalline be yellow copper structure; Like Fig. 2, resulting quantum dot is carried out electron spectroscopy analysis calculate Cu: the atomic ratio of In: Se is 1: 1.08: 2.12.
Embodiment 2:
1) takes by weighing 44.2mg (0.2mmol) In (Cl)
3, 19.1mg (0.1mmol) CuI and adds 1.43ml (6mmol) lauryl mercaptan in a 25ml four-hole boiling flask, and the octadecylene of 8ml stirs 30min vacuumizing the condition lower magnetic force, is dissolved to clarification fully to positively charged ion precursor liquid, obtains Cu
+, In
3+Cation precursor solution; Take by weighing 47.4mg (0.6mmol) simple substance Se, in a single port round-bottomed bottle, and add the octadecylene of 450ul (1.8mmol) TBP, 3ml, excusing from death is dissolved to clarification and obtains body fluid before the Se.
2) in system, recharge argon gas, with Cu
+, In
3+Cation precursor solution is rapidly heated from room temperature and is heated to 200 ℃, injects the Se precursor solution, removes thermal source behind the reaction 15min and is cooled to room temperature, and centrifugal purification obtains CuInSe
2Quantum dot;
As shown in Figure 1, the CuInSe of acquisition
2The XRD figure of quantum dot spectrum proved resulting nanocrystalline be yellow copper structure; Like Fig. 2, resulting quantum dot is carried out electron spectroscopy analysis calculate Cu: the atomic ratio of In: Se is 1: 0.99: 2.04.
Embodiment 3:
1) takes by weighing 148.7mg (0.3mmol) InI
3, 12.3mg (0.1mmol) CuAc and adds 1.35ml (4mmol) Stearyl mercaptan in a 25ml four-hole boiling flask, and the octadecylene of 7ml stirs 30min vacuumizing the condition lower magnetic force, is dissolved to clarification fully to positively charged ion precursor liquid, obtains Cu
+, In
3+Cation precursor solution; Take by weighing 632mg (0.8mmol) simple substance Se, in a single port round-bottomed bottle, and add the octadecylene of 600ul (2.4mmol) TBP, 4ml, excusing from death is dissolved to clarification and obtains body fluid before the Se.
2) in system, recharge argon gas, with Cu
+, In
3+Cation precursor solution quickly heats up to 250 ℃ from room temperature, injects the Se precursor solution, removes thermal source behind the reaction 60min and is cooled to room temperature, and centrifugal purification obtains CuInSe
2Quantum dot;
As shown in Figure 1, the CuInSe of acquisition
2The XRD figure of quantum dot spectrum proved resulting nanocrystalline be yellow copper structure; Like Fig. 2, resulting quantum dot is carried out electron spectroscopy analysis calculate Cu: the atomic ratio of In: Se is 1: 1.04: 2.07.
Embodiment 4:
1) takes by weighing 29.2mg (0.1mmol) In (Ac)
3, 9.9mg (0.1mmol) CuCl and adds 1.39ml (8mmol) octyl mercaptan in a 25ml four-hole boiling flask, and the octadecylene of 6ml stirs 30min vacuumizing the condition lower magnetic force, is dissolved to clarification fully to positively charged ion precursor liquid, obtains Cu
+, In
3+Cation precursor solution; Take by weighing 31.6mg (0.4mmol) simple substance Se, in a single port round-bottomed bottle, and add the octadecylene of 536ul (1.2mmol) TOP, 2ml, excusing from death is dissolved to clarification and obtains body fluid before the Se.Take by weighing 109.74mg (0.5mmol) Zn (Ac)
2In a single port round-bottomed bottle, add the octadecylene of 1ml (3.1mmol) oleyl amine, 4ml, be heated to the dissolving clarification and obtain the preceding body fluid of zinc.
2) in system, recharge argon gas, with Cu
+, In
3+Cation precursor solution is rapidly heated from room temperature and is heated to 230 ℃, injects the Se precursor solution, reaction 45min.
3) with the CuInSe that obtains
2Quantum dot solution is cooled to 230 ℃, and dropwise dripping concentration then is the zinc precursor solution of 0.1M, behind the reacting by heating 30min, removes thermal source and naturally cools to the room temperature centrifugal purification and obtain CuInSe
2/ ZnS nuclear shell structure quantum point.
As shown in Figure 3, the CuInSe of acquisition
2The fluorescent emission wavelength of/ZnS nuclear shell structure quantum point is 700nm, and fluorescence quantum efficiency is 33.4%.
Embodiment 5:
1) takes by weighing 44.2mg (0.2mmol) In (Cl)
3, 19.1mg (0.1mmol) CuI and adds 1.43ml (6mmol) lauryl mercaptan in a 25ml four-hole boiling flask, and the octadecylene of 8ml stirs 30min vacuumizing the condition lower magnetic force, is dissolved to clarification fully to positively charged ion precursor liquid, obtains Cu
+, In
3+Cation precursor solution; Take by weighing 47.4mg (0.6mmol) simple substance Se, in a single port round-bottomed bottle, and add the octadecylene of 450ul (1.8mmol) TBP, 3ml, excusing from death is dissolved to clarification and obtains body fluid before the Se.Take by weighing 316.2mg (0.5mmol) Zn (SA)
2In a single port round-bottomed bottle, add the octadecylene of 1ml oleic acid, 4ml, be heated to the dissolving clarification and obtain the preceding body fluid of zinc.
2) in system, recharge argon gas, with Cu
+, In
3+Cation precursor solution is rapidly heated from room temperature and is heated to 200 ℃, injects the Se precursor solution, reaction 15min.
3) with the CuInSe that obtains
2Quantum dot solution is cooled to 210 ℃, and dropwise dripping concentration then is the zinc precursor solution of 0.1M, behind the reacting by heating 45min, removes thermal source and naturally cools to the room temperature centrifugal purification and obtain CuInSe
2/ ZnS nuclear shell structure quantum point.
As shown in Figure 4, the CuInSe of acquisition
2The fluorescent emission wavelength of/ZnS nuclear shell structure quantum point is 820nm, and fluorescence quantum efficiency is 24.5%.
Embodiment 6:
1) takes by weighing 148.7mg (0.3mmol) InI
3, 12.3mg (0.1mmol) CuAc and adds 1.35ml (4mmol) Stearyl mercaptan in a 25ml four-hole boiling flask, and the octadecylene of 7ml stirs 30min vacuumizing the condition lower magnetic force, is dissolved to clarification fully to positively charged ion precursor liquid, obtains Cu
+, In
3+Cation precursor solution; Take by weighing 632mg (0.8mmol) simple substance Se, in a single port round-bottomed bottle, and add the octadecylene of 600ul (2.4mmol) TBP, 4ml, excusing from death is dissolved to clarification and obtains body fluid before the Se.Take by weighing 316.2mg (0.5mmol) Zn (SA)
2In a single port round-bottomed bottle, add the octadecylene of 1ml oleyl amine, 4ml, be heated to the dissolving clarification and obtain the preceding body fluid of zinc.
2) in system, recharge argon gas, with Cu
+, In
3+Cation precursor solution quickly heats up to 250 ℃ from room temperature, injects the Se precursor solution, reaction 60min.
3) with the CuInSe that obtains
2Quantum dot solution is cooled to 230 ℃, and dropwise dripping concentration then is the zinc precursor solution of 0.1M, behind the reacting by heating 60min, removes thermal source and naturally cools to the room temperature centrifugal purification and obtain CuInSe
2/ ZnS nuclear shell structure quantum point.
As shown in Figure 5, the CuInSe of acquisition
2The fluorescent emission wavelength of/ZnS nuclear shell structure quantum point is 960nm, and fluorescence quantum efficiency is 19.8%.
Claims (6)
1. yellow copper structure CuInSe
2The preparation method of quantum dot is characterized in that step is following:
1) preparation contains Cu
+, In
3+Cation precursor solution and Se precursor solution;
2) under argon shield, will contain Cu
+, In
3+Cation precursor solution be heated to 200～250 ℃ after, inject the Se precursor solution, behind reaction 15～60min, remove thermal source and naturally cool to room temperature;
3) centrifugal purification promptly obtains the CuInSe of yellow copper structure
2Quantum dot.
2. preparation method as claimed in claim 1; It is characterized in that: described step 1) is as the indium source with indium acetate, indium chloride or indium iodide; With cuprous acetate, cuprous chloride or cuprous iodide as the copper source; With backbone length be the saturated fatty mercaptan of 8～18 carbon atoms as part and activity inhibitor, with octadecylene as reaction solvent, the Cu of the clear that under the condition of protection of inert gas, obtains through magnetic agitation 30min heating
+, In
3+Cation precursor solution.
3. preparation method as claimed in claim 2 is characterized in that: Cu in the described cation precursor solution
+, In
3+Mol ratio is 1: 1～1: 3, Cu
+, In
3+Cationic and with the mol ratio of part be 1: 10～1: 40.
4. preparation method as claimed in claim 1; It is characterized in that: described step 1) Se precursor solution is to be the Se source with Se simple substance; With three normal-butyl phosphorus or three n-octyl phosphorus is part; The mol ratio of Se and part is 1: 3, and is body fluid before the Se of the solvent supersonic dissolving 0.2M that obtains clear with the octadecylene.Said step 2) the Se precursor and the Cu that add in
+, In
3+Cationic and molar ratio is 2: 1.
5. adopt the yellow copper structure CuInSe of claim 1
2The preparation method of quantum dot prepares CuInSe
2The method of/ZnS nuclear shell structure quantum point; It is characterized in that: in step 2); After injecting Se precursor solution reaction 15～60min, temperature of reaction is transferred to 190～230 ℃, drip the zinc precursor solution; React and remove thermal source behind the 30-60min and naturally cool to room temperature, centrifugal purification obtains yellow copper structure CuInSe
2/ ZnS nuclear shell structure quantum point.
6. preparation method as claimed in claim 5; It is characterized in that: described zinc precursor solution is to be the zinc source with Zinic stearas or zinc acetate; With oleic acid or oleyl amine is part, and the mol ratio of zinc source and part is 1: 6, is body fluid before the zinc of the 0.1M for preparing of solvent heating with the octadecylene.
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| CN103030118A (en) * | 2012-12-26 | 2013-04-10 | 中北大学 | Preparation method of pattern and size controllable CuInSe2 nanoparticles |
| CN103213956A (en) * | 2013-02-25 | 2013-07-24 | 上海理工大学 | Preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles |
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