CN102643643A - Preparation method for CuInS2 or/and CuInS2/ZnS core-shell quantum dot with zinc blende structure - Google Patents
Preparation method for CuInS2 or/and CuInS2/ZnS core-shell quantum dot with zinc blende structure Download PDFInfo
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Abstract
The invention relates to a preparation method for a water-soluble CuInS2 or/and CuInS2/ZnS core-shell quantum dot with a zinc blende structure. The preparation method comprises the following steps of: preparing In precursor solution and Cu precursor solution under the protection of argon, heating the In precursor solution and the Cu precursor solution to 200-250 DEG C from a room temperature with a temperature-rising speed of 1 DEG C/s, and reacting for 30-60 minutes to obtain the quantum dot solution of CuInS2; and rapidly injecting zinc precursor solution, reacting for 30-60 minutes at 180-220 DEG C, naturally cooling to the room temperature, and centrifugally purifying to obtain the quantum dot with the CuInS2/ZnS core-shell structure. The obtained water-soluble CuInS2 quantum dot has a zinc blende crystal structure, and the atomic ratio of Cu to In to S is slightly higher than 1: 1: 2; and the fluorescence emission peak range of the CuInS2/ZnS core-shell quantum dot is from 538 to 760 nm, and the fluorescence quantum yield is 22-39%. Via the preparation method disclosed by the invention, water-soluble quantum dots of CuInS2 and CuInS2/ZnS are prepared by taking PEG (polyethylene glycol) as a solvent, and taking sulfhydryl fatty alcohol as a ligand, a sulphur source and an activity inhibitor on the basis of colloidal chemical synthesis method for an oil-soluble quantum dot; and the step of biocompatibility modification is omitted for a biomedical application in later stage.
Description
Technical field
The present invention relates to compound semiconductor nano material preparation technical field, particularly a kind of CuInS of water-soluble zincblende lattce structure
2And CuInS
2/ ZnS nuclear shell structure quantum point and preparation method thereof.
Background technology
(quantum dot is that its size is generally less than 10nm by the seldom atom or the molecular aggregate of number QD) to quantum dot, is generally spherical or type spherical.Since the size of quantum dot near in addition less than exciton (electron-hole pair) the Bohr radius of corresponding semiconductor body phase material; The electronics and the hole that produce when being stimulated are limited in narrow and small three-dimensional space; Thereby show unique quantum dimensional effect, dielectric confinement effect, surface effects and macro quanta tunnel effect, have unique optical property.Quantum dot has quantized valence band and conduction band, and its energy depends on the size of nanocrystal.Quantizedly can cause emmission spectrum discrete, that depend on the quantum dot size with energy, thus be a kind of can be through the radiator of varying sized accurate adjusting fluorescent emission wavelength.Compare with traditional organic fluorescence element, the photoluminescence property of quantum dot has following characteristic: the excitation spectrum wide ranges, and emmission spectrum is adjustable; Emission peak is narrow and symmetrical and do not have a hangover; Stokes shift is big, and anti-photodegradation and chemical degradation capabilities are stronger, fast light bleaching.At present, the research of quantum dot mainly concentrates on II-VI group element compound (like ZnS, CdSe) quantum dot, III-V group element compound (like InP, InAs and GaAs) quantum dot, and I-III-VI group element compound (like CuInSe and CuInS) quantum dot.
Along with the continuous cross development of subjects such as quantum dot and molecular biology, medical diagnostics, the application of near-infrared quantum dots in bio-imaging shows great potential.Visible region (400-700nm) imaging can receive the absorption of endogenous material in the biological tissue, the influence of scattering; And scattering, absorption and the autofluorescence background of near infrared region (700-900nm) when imaging tissue are all lower; And can obtain maximum penetration; Carry out the deep tissues imaging, therefore select near-infrared quantum dots to be applied to in-vivo imagings such as live body diagnosis and fluorescence imaging and detect.Wherein the research of II-VI family element near-infrared quantum dots is comparatively ripe; But generally all contain heavy metal elements such as Cd, Hg and Pb; Be easy to show bio-toxicity, limited further developing of it, especially in the further application of living microbe diagnostic field in organ enrichments such as liver, spleens.At present the researchist has prepared the fluorescent emission wavelength and is positioned at near-infrared region (650～1100nm) III-V family and I-III-VI group element compound oil soluble quantum dot are like InP/ZnS, CuInSe and CuInS
2Quantum dot is for quantum dot provides possibility in the application of living microbe diagnostic field.Because the needed reacting precursor of preparation III-V group element compound is like three (front three is silica-based) phosphorus (P (TMS)
3), expensive and poor chemical stability, required experiment condition is harsh, be unfavorable for mass production, so the I-III-VI group element compound becomes the first-selection of research, especially CuInS
2Quantum dot becomes the focus of research gradually over nearly 5 years.
At present for CuInS<sub >2</sub>The research of quantum dot still is in the preparation research stage, and mainly concentrates on oil soluble quantum dot aspect.The oil soluble CuInS of the comparative maturity that development in recent years is got up<sub >2</sub>The compound method of quantum dot mainly contains thermal decomposition method and hot injection.Like Peng etc. with 1-Dodecyl Mercaptan (DDT) as Cu<sup >+</sup>Activity inhibitor, the sulphur powder is dissolved in the octadecylene In, the Cu mixed precursor solution that inject heat has successfully prepared CuInS<sub >2</sub>And CuInS<sub >2</sub>/ ZnS quantum dot is [referring to article<formation of High Quality I-III-VI Semiconductor Nanocrystals by Tuning Relative Reactivity of Cationic Precursors>]; Reiss etc. are mixed and heated to 240 ℃ of reactions with DDT as sulphur source and In, the Cu precursor solution of reaction and obtain CuInS<sub >2</sub>And CuInS<sub >2</sub>/ ZnS quantum dot is [referring to article<highly Luminescent CuInS2/ZnS Core/ShellNanocrystals:Cadmium-Free Quantum Dots for In Vivo Imaging>].Because the CuInS that present most of compound method obtains<sub >2</sub>The fluorescence efficiency of quantum dot is generally lower, general less than 5%.In order further to improve CuInS<sub >2</sub>The fluorescence efficiency of quantum dot strengthens its photochemical stability, at present comparative maturity and be through at CuInS by the technology that extensively adopts<sub >2</sub>The inorganic shell of quantum dot surface growth ZnS, thereby the nano particle of formation nucleocapsid structure.
Though through above-mentioned technique means synthetic oil soluble CuInS
2/ ZnS has better fluorescence; But mostly the surface ligand of the quantum dot of gained is alkyl sulfhydryl; Like hexyl mercaptans, sulfydryl dodecyl, sulfydryl octadecane etc., make quantum dot can not directly be used for biological in-vivo imaging, need carry out the surface hydrophilic modification to it and change with kind biocompatibility.In addition, (SH) stronger with Cu and In Atomic coordinate reactive force, common method of carrying out ligand exchange with mercaptan carboxylic acid's class or sulfydryl alcohols part and quantum dot surface ligand can not effectively realize CuInS because sulfydryl
2And CuInS
2The biocompatibility modification of/ZnS quantum dot has limited its application.For this reason, we have invented a kind of method of directly synthetic high fluorescence quality water-soluble quantum dot, have simplified the synthetic and application of quantum dot.
Summary of the invention
We are at the preparation oil soluble CuInS that uses for reference existing public reported
2And CuInS
2On/ZnS technology of quantum dots the basis, some technological improvements have been carried out, the directly synthetic CuInS that has prepared water miscible zincblende lattce structure
2And CuInS
2/ ZnS nuclear shell structure quantum point, the CuInS of gained
2/ ZnS quantum dot need not to carry out the surface hydrophilic modification and promptly can be applicable to the od-ray diagnosis research.Be compared to general oil-soluble synthetic and further modification and use, this technological synthesis technique is simple, and repeatable strong, the gained quantum dot has higher fluorescence efficiency, and is that the application that later living microbe is diagnosed lays the foundation.The objective of the invention is to propose a kind of CuInS of water-soluble zincblende lattce structure
2And CuInS
2/ ZnS nuclear shell structure quantum point and preparation method thereof is further simplified and is improved present CuInS
2And CuInS
2The preparation technology of/ZnS nuclear shell structure quantum point.
Technical scheme of the present invention is following:
A kind of water-soluble zincblende lattce structure CuInS
2The preparation method of quantum dot is characterized in that comprising the steps:
1) takes by weighing copper source compound, indium source compound and sulfydryl Fatty Alcohol(C12-C14 and C12-C18), and in the four-hole boiling flask of 50ml, mix, under magnetic agitation and vacuum condition, solution is heated to 100 ℃ keeps 30min to clear state with polyoxyethylene glycol;
2) under argon shield, the reaction solution that the first step is obtained with the temperature rise rate of 1 ℃/s is heated to 200～250 ℃, removes thermal source behind reaction 30～60min and naturally cools to room temperature; Cu in the reaction solution
+, In
3+Mol ratio is 1: 1～1: 2, and the mol ratio of positively charged ion and sulfydryl Fatty Alcohol(C12-C14 and C12-C18) is 1: 10～1: 20;
3) centrifugal purification promptly obtains the CuInS of zincblende lattce structure
2Quantum dot.
Described step 1) reaction solution is to be the copper source with cuprous iodide or cuprous chloride; With indium acetate or indium chloride is the indium source; With backbone length is that the sulfydryl Fatty Alcohol(C12-C14 and C12-C18) of 6～11 carbon atoms is sulphur source, part and activity inhibitor; With molecular weight is that 400～2000 polyoxyethylene glycol is a solvent, the clarifying Cu that obtains 100 ℃ of magnetic agitation 30min heating
+, In
3+Cationoid reaction liquid.
Described step 1) gets final product material dissolution because polyoxyethylene glycol as this dissolvant of reaction system, does not have remarkable influence to the performance of products made thereby.
A kind of water-soluble zincblende lattce structure CuInS
2/ ZnS nuclear shell structure quantum point preparation method is characterized in that: at preparation CuInS
2The step 2 of quantum dot), reaction solution is heated to 200～250 ℃, behind reaction 30～60min; Temperature of reaction is transferred to 180～220 ℃; Inject rapidly the zinc precursor solution, react and remove thermal source behind 30～60min and naturally cool to room temperature, centrifugal purification obtains zincblende lattce structure CuInS
2/ ZnS nuclear shell structure quantum point.
Described zinc precursor solution is to be the zinc source with Zinic stearas or zinc acetate, is that 400 polyoxyethylene glycol is that the solvent heating prepares with molecular weight, and the concentration of zinc precursor solution is 0.1M.
The CuInS that the present invention obtains
2Quantum dot carries out X-ray diffraction (XRD) and electron spectroscopy analysis (EDX).Can find out made CuInS 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 28.59 °, 47.52 ° and 55.84 °, correspond respectively to (111) in the zinc blende crystal structure, (220) and (222) prove the CuInS for preparing
2Quantum dot has the zinc blende crystal structure.Characterize the CuInS of preparation through electron spectroscopy analysis (EDX)
2The atom of quantum dot is formed; Can draw from accompanying drawing 2; The atomic ratio of Cu: In: S be 1.02: 1: 2.13～1.09: 1: 2.21 a little more than 1: 1: 2 stoichiometric ratio; This possibly be because sulfydryl fat alkanol carries out coordination on the quantum dot surface, causes the surface to be rich in the S atom, the CuInS that makes preparation
2Middle S atom content is slightly higher than theoretical value.
The water-soluble zincblende lattce structure CuInS that the present invention obtains
2Scope 538～the 760nm of the fluorescent emission peak position of/ZnS core-shell quanta dots, fluorescence quantum yield are 22～39%.
Cu in the reaction solution of the present invention
+, In
3+Mol ratio is 1: 1～1: 2, and the mol ratio of positively charged ion and sulfydryl Fatty Alcohol(C12-C14 and C12-C18) is 1: 10～1: 20.The sulfydryl Fatty Alcohol(C12-C14 and C12-C18) discharges sulphur easy decomposition the under hot conditions, so the decomposition of sulfydryl Fatty Alcohol(C12-C14 and C12-C18) can be to generate CuInS in the system
2Quantum dot provides the sulphur source.In addition, because its end sulfydryl (SH) and In
3+, Cu
+Have good coordination and promptly form Cu
+～SH-(CH
2)
11OH and In
3+[～SH-(CH
2)
11OH]
nTherefore mixture can be used as a kind of effective part and activity inhibitor prepares In, Cu precursor solution, and can effectively prevent nanocrystalline reunion under hot conditions.Since sulfydryl Fatty Alcohol(C12-C14 and C12-C18) two ends be respectively the end sulfydryl (SH) with terminal hydroxy group (OH), the end sulfydryl (SH) and nanocrystalline in Cu
+And In
3+Closely coordination, terminal hydroxy group makes prepared quantum dot surface be rich in hydrophilic radical-OH, possess hydrophilic property has good dispersiveness in aqueous environment such as PEG, alcohol.Because polyoxyethylene glycol is as this dissolvant of reaction system, the performance of products made thereby there is not remarkable influence, thus there is not strict quantitative limitation, preferably about 5ml.In this step, remove oxygen and moisture in the system through the means that vacuumize, avoid In
3+And Cu
+Hydrolysis under hot conditions.
Zinc precursor solution of the present invention is to be the zinc source with Zinic stearas or zinc acetate, is that 400 polyoxyethylene glycol is that the solvent heating prepares with molecular weight, and the concentration of zinc precursor solution is 0.1M.
The present invention is because temperature of reaction system is all higher, so excessive sulfydryl Fatty Alcohol(C12-C14 and C12-C18) discharges sulphur atom through thermolysis in the system, is at CuInS simultaneously
2The quantum dot surface forms the ZnS shell sulphur source is provided, and obtains CuInS through centrifugal purification at last
2/ ZnS quantum dot, and calculate fluorescence quantum efficiency.
The method of calculation of the calculating fluorescence quantum efficiency that the present invention adopts are following:
The present invention adopts dilute solution fluorescence reference installation to made CuInS
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 CuInS
2The fluorescence quantum yield of/ZnS nuclear shell structure quantum point.CuInS wherein
2/ ZnS nuclear shell structure quantum point is dissolved in the ethanol, and absorbancy transfers between 0.05～0.1 at the 600nm place with it.
The present invention compared with prior art; 1), combined the colloid chemistry synthesis method of the preparation oil soluble quantum dot of present comparative maturity biggest advantage and difference are:; Through being solvent with PEG, the sulfydryl Fatty Alcohol(C12-C14 and C12-C18) has prepared water miscible CuInS as sulphur source, part and activity inhibitor
2And CuInS
2/ ZnS quantum dot need not to carry out the surface hydrophilic modification and promptly can be applicable to the od-ray diagnosis research; 2), the water-soluble zincblende lattce structure CuInS of synthetic of the present invention
2Scope 538～the 760nm of the fluorescent emission peak position of/ZnS core-shell quanta dots, fluorescence quantum yield are 22～39%, can satisfy the requirement of bio-medical diagnosis; 3), adopt simple one kettle way, synthesis cycle is short, the simple and good reproducibility of technology is beneficial to mass production.
Description of drawings
Made water-soluble zincblende lattce structure CuInS among Fig. 1: the embodiment 12,3
2The X-ray diffraction of quantum dot (XRD) collection of illustrative plates;
Made water-soluble zincblende lattce structure CuInS among Fig. 2: the embodiment 12,3
2Electron energy analysis (EDX) collection of illustrative plates of quantum dot;
Made CuInS among Fig. 3: the embodiment 4
2The fluorescent emission of/ZnS nuclear shell structure quantum point and uv absorption spectrum synoptic diagram;
Made CuInS among Fig. 4: the embodiment 5
2The fluorescent emission of/ZnS nuclear shell structure quantum point and uv absorption spectrum synoptic diagram;
Made CuInS among Fig. 5: the embodiment 6
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 In
3+, Cu
+Body fluid before cation precursor reaction solution and the zinc;
2) under argon shield, the reaction solution that the first step is obtained with the temperature rise rate of 1 ℃/s is heated to 200～250 ℃, removes thermal source behind reaction 30～60min and naturally cools to room temperature, and centrifugal purification promptly obtains the CuInS of zincblende lattce structure
2Quantum dot.If preparation CuInS
2/ ZnS nuclear shell structure quantum point does not then carry out the centrifugal purification operation in this step, directly carry out next step reaction.
3) temperature of reaction is transferred to 180～220 ℃, inject the zinc precursor solution rapidly, remove thermal source behind reaction 30～60min and naturally cool to room temperature, centrifugal purification obtains zincblende lattce structure CuInS
2/ ZnS nuclear shell structure quantum point.
Embodiment 1:
1) takes by weighing 29.2mg (0.1mmol) In (Ac)
3, 19.1mg (0.1mmol) CuI and 0.49g (3mmol) sulfydryl octanol place a 50ml four-hole boiling flask, and add the PEG-400 of 5ml, under magnetic agitation and vacuum condition, are heated to 100 ℃ and keep 30min and clarify to reaction solution, obtain In
3+, Cu
+Cation precursor solution;
2) in system, recharge argon gas, with the temperature rise rate of 1 ℃/s with In
3+, Cu
+Cation precursor solution is heated to 230 ℃ of reactions from room temperature and removes thermal source behind the 30min and be cooled to room temperature, and centrifugal purification obtains CuInS
2Quantum dot.
As shown in Figure 1, the CuInS of acquisition
2The XRD figure of quantum dot spectrum Shanghai Stock Exchange clear resulting nanocrystalline be zincblende lattce structure; Like Fig. 2, calculate Cu by electron spectroscopy analysis: In: the atomic ratio of S is 1.09: 1: 2.21.
Embodiment 2:
1) takes by weighing 58.4mg (0.2mmol) In (Ac)
3, 9.9mg (0.1mmol) CuCl adds the PEG-800 of 0.83ml (6mmol) sulfydryl hexanol, 5ml in a four-hole boiling flask, under magnetic agitation and vacuum condition, be heated to 100 ℃ and keep 30min and clarify to reaction solution, obtains In
3+, Cu
+Cation precursor solution;
2) in system, recharge argon gas, with the temperature rise rate of 1 ℃/s with In
3+, Cu
+Cation precursor solution is heated to 200 ℃ of reactions from room temperature and removes thermal source behind the 45min and be cooled to room temperature, and centrifugal purification obtains CuInS
2Quantum dot.
Characterize the CuInS of acquisition like Fig. 1 method
2The XRD figure of quantum dot spectrum Shanghai Stock Exchange clear resulting nanocrystalline be zincblende lattce structure; Like Fig. 2, calculate Cu by electron spectroscopy analysis: In: the atomic ratio of S is 1.02: 1: 2.13.
Embodiment 3:
1) takes by weighing 44.2mg (0.2mmol) InCl3; 9.9mg (0.1mmol) CuCl and 0.62g (3mmol) sulfydryl hendecanol is in a four-hole boiling flask, and adds the PEG-2000 of 5ml, under magnetic agitation and vacuum condition; Be heated to 100 ℃ and keep 30min and clarify, obtain In to reaction solution
3+, Cu
+Cation precursor solution;
2) in system, recharge argon gas, with the temperature rise rate of 1 ℃/s with In
3+, Cu
+Cation precursor solution is heated to 250 ℃ of reactions from room temperature and removes thermal source behind the 60min and be cooled to room temperature, and centrifugal purification obtains CuInS
2Quantum dot.
Characterize the CuInS of acquisition like Fig. 1 method
2The XRD figure of quantum dot spectrum Shanghai Stock Exchange clear resulting nanocrystalline be zincblende lattce structure; Like Fig. 2, calculate Cu by electron spectroscopy analysis: In: the atomic ratio of S is 1.04: 1: 2.15.
Embodiment 4:
1) takes by weighing 29.2mg (0.1mmol) In (Ac)
3, 19.1mg (0.1mmol) CuI and 0.49g (3mmol) sulfydryl octanol and add the PEG-400 of 5ml in a 50ml four-hole boiling flask, under magnetic agitation and vacuum condition, be heated to 100 ℃ and keep 30min and clarify to reaction solution, obtain In
3+, Cu
+Cation precursor solution; Take by weighing 87.79mg (0.4mmol) Zn (Ac)
2In a single port round-bottomed bottle, add 4ml PEG-400, be heated to clarification at 80 ℃, obtain the preceding body fluid of zinc.
2) in system, recharge argon gas, with the temperature rise rate of 1 ℃/s with In
3+, Cu
+Cation precursor solution carries out three-step reaction after room temperature is heated to 230 ℃ of reaction 30min.
3) temperature of reaction is transferred to 200 ℃, inject body fluid before the zinc then rapidly, behind the reacting by heating 30min, remove thermal source and naturally cool to the room temperature centrifugal purification and obtain CuInS
2/ ZnS nuclear shell structure quantum point.
As shown in Figure 3, the CuInS of acquisition
2The fluorescent emission wavelength of/ZnS nuclear shell structure quantum point is 538nm, and fluorescence quantum efficiency is 39%.
Embodiment 5:
1) takes by weighing 58.4mg (0.2mmol) In (Ac)
3, 9.9mg (0.1mmol) CuCl adds the PEG-800 of 0.83ml (6mmol) sulfydryl hexanol, 5ml in a four-hole boiling flask, under magnetic agitation and vacuum condition, be heated to 100 ℃ and keep 30min and clarify to reaction solution, obtains In
3+, Cu
+Cation precursor solution; Take by weighing 252.93mg (0.4mmol) Zn (SA)
2In a single port round-bottomed bottle, add 4ml PEG-400, be heated to clarification at 80 ℃, obtain the preceding body fluid of zinc.
2) in system, recharge argon gas, with the temperature rise rate of 1 ℃/s with In
3+, Cu
+Cation precursor solution carries out three-step reaction after room temperature is heated to 200 ℃ of reaction 45min.
3) temperature of reaction is transferred to 180 ℃, inject the zinc precursor solution then rapidly, behind the reacting by heating 45min, remove thermal source and naturally cool to the room temperature centrifugal purification and obtain CuInS
2/ ZnS nuclear shell structure quantum point.
As shown in Figure 4, the CuInS of acquisition
2The fluorescent emission wavelength of/ZnS nuclear shell structure quantum point is 675nm, and fluorescence quantum efficiency is 25.9%.
Embodiment 6:
1) takes by weighing 44.2mg (0.2mmol) InCl3; 9.9mg (0.1mmol) CuCl and 0.62g (3mmol) sulfydryl hendecanol is in a four-hole boiling flask, and adds the PEG-2000 of 5ml, under magnetic agitation and vacuum condition; Be heated to 100 ℃ and keep 30min and clarify, obtain In to reaction solution
3+, Cu
+Cation precursor solution; Take by weighing 252.93mg (0.4mmol) Zn (SA) 2 in a single port round-bottomed bottle, add 4ml PEG-400, be heated to clarification, obtain the preceding body fluid of zinc at 80 ℃.
2) in system, recharge argon gas, with the temperature rise rate of 1 ℃/s with In
3+, Cu
+Cation precursor solution carries out three-step reaction after room temperature is heated to 250 ℃ of reaction 60min.
3) temperature of reaction is transferred to 220 ℃, inject body fluid before the zinc then rapidly, behind the reacting by heating 60min, remove thermal source and naturally cool to the room temperature centrifugal purification and obtain CuInS
2/ ZnS nuclear shell structure quantum point.
As shown in Figure 5, the CuInS of acquisition
2The fluorescent emission wavelength of/ZnS nuclear shell structure quantum point is 760nm, and fluorescence quantum efficiency is 22%.
Claims (4)
1. water-soluble zincblende lattce structure CuInS
2The preparation method of quantum dot is characterized in that step is following:
1) takes by weighing copper source compound, indium source compound and sulfydryl Fatty Alcohol(C12-C14 and C12-C18), and in the four-hole boiling flask of 50ml, mix, under magnetic agitation and vacuum condition, solution is heated to 100 ℃ keeps 30min to clear state with polyoxyethylene glycol; Cu
+, In
3+Mol ratio is 1: 1～1: 2; Cu
+, In
3+Cationic and with the mol ratio of sulfydryl Fatty Alcohol(C12-C14 and C12-C18) be 1: 10～1: 20;
2) under argon shield, the reaction solution that the first step is obtained with the temperature rise rate of 1 ℃/s is heated to 200～250 ℃, reacts to remove thermal source behind 30～60min and naturally cool to room temperature again;
3) centrifugal purification promptly obtains the CuInS of zincblende lattce structure
2Quantum dot.
2. preparation method as claimed in claim 1; It is characterized in that: described step 1) reaction solution is to be the copper source with cuprous iodide or cuprous chloride; With indium acetate or indium chloride is the indium source; With backbone length is that the sulfydryl Fatty Alcohol(C12-C14 and C12-C18) of 6～11 carbon atoms is sulphur source, part and activity inhibitor, is that 400～2000 polyoxyethylene glycol is a solvent with molecular weight, the clarifying Cu that obtains 100 ℃ of magnetic agitation 30min heating
+, In
3+Cationoid reaction liquid.
3. adopt the zincblende lattce structure CuInS of claim 1
2The preparation method of quantum dot prepares CuInS
2The method of/ZnS nuclear shell structure quantum point; It is characterized in that: in step 2), reaction solution is heated to 200～250 ℃, behind reaction 30～60min; Temperature of reaction is transferred to 180～220 ℃; Inject rapidly the zinc precursor solution, react and remove thermal source behind 30～60min and naturally cool to room temperature, centrifugal purification obtains zincblende lattce structure CuInS
2/ ZnS nuclear shell structure quantum point.
4. preparation method as claimed in claim 4; It is characterized in that described zinc precursor solution is is the zinc source with Zinic stearas or zinc acetate; With molecular weight is that 400 polyoxyethylene glycol is a solvent, and heating prepares under 80 ℃ of conditions, and the concentration of zinc precursor solution is 0.1M.
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| CN104513663A (en) * | 2013-09-27 | 2015-04-15 | 深圳先进技术研究院 | Near-infrared copper-indium-selenium quantum dot and preparation method thereof |
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| CN105219380A (en) * | 2015-10-20 | 2016-01-06 | 广东昭信光电科技有限公司 | A kind of high quality colloid is without the synthetic method of cadmium quantum dot |
| CN110066652A (en) * | 2018-01-22 | 2019-07-30 | Tcl集团股份有限公司 | A kind of quantum dot and preparation method thereof |
| CN110105946A (en) * | 2019-06-03 | 2019-08-09 | 西北师范大学 | 2 mercapto ethanol is the synthesis and application of the indium sulphur ternary quantum dots of ligand |
| CN110105946B (en) * | 2019-06-03 | 2021-12-21 | 西北师范大学 | Synthesis and application of copper-indium-sulfur ternary quantum dot with 2-mercaptoethanol as ligand |
| CN111977685A (en) * | 2020-06-09 | 2020-11-24 | 河南大学 | Preparation method of sodium ion battery negative electrode material |
| CN111977685B (en) * | 2020-06-09 | 2022-09-02 | 河南大学 | Preparation method of sodium ion battery negative electrode material |
| CN115340863A (en) * | 2022-06-29 | 2022-11-15 | 河北大学 | Near-infrared core-shell structure quantum dot CuInS 2 Method for synthesizing/ZnS |
| CN115340863B (en) * | 2022-06-29 | 2023-11-14 | 河北大学 | Near infrared core-shell structure quantum dot CuInS 2 Method for synthesizing ZnS |
| CN115340866A (en) * | 2022-08-30 | 2022-11-15 | 北华大学 | CuAlInS quantum dot and preparation method thereof |
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