WO2012167398A1 - 一种制备核壳纳米粒子及其溶液的方法 - Google Patents

一种制备核壳纳米粒子及其溶液的方法 Download PDF

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WO2012167398A1
WO2012167398A1 PCT/CN2011/000950 CN2011000950W WO2012167398A1 WO 2012167398 A1 WO2012167398 A1 WO 2012167398A1 CN 2011000950 W CN2011000950 W CN 2011000950W WO 2012167398 A1 WO2012167398 A1 WO 2012167398A1
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shell
core
solution
mercaptan
nanoparticles
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WO2012167398A8 (zh
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付敏
刘涛
韩德滋
卢华昌
马熠龙
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拜尔技术工程（上海）有限公司
拜尔技术服务有限公司
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Priority to CN201180070699.3A priority Critical patent/CN103582690B/zh
Priority to PCT/CN2011/000950 priority patent/WO2012167398A1/zh
Priority to PCT/EP2012/060661 priority patent/WO2012168279A1/en
Publication of WO2012167398A1 publication Critical patent/WO2012167398A1/zh
Publication of WO2012167398A8 publication Critical patent/WO2012167398A8/zh

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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/621—Chalcogenides
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C30B29/48—AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
    • C—CHEMISTRY; METALLURGY
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to a method of preparing core-shell nanoparticles and solutions thereof. Background technique
  • Inorganic semiconductor nanoparticles have the characteristics of stable performance, wide excitation spectrum, narrow fluorescence spectrum, and small luminescence properties affected by the surrounding environment. They can effectively replace organic luminescent materials in solar cells, light-emitting diodes, fluorescent probes, biomarkers, and anti-counterfeiting labels. , functional film, laser, electronic communication and other fields have been widely used.
  • inorganic semiconductor nanoparticles contain cadmium, arsenic, lead, selenium and other elements, which are highly toxic and pollute the environment, which is not conducive to commercial applications. Therefore, semiconductor nanoparticles with low toxicity or low toxicity, high solar absorption coefficient and high light stability have been extensively studied, such as IB-IIIA-VIA group nanoparticles or IIB-IB-IIIA-VIA group nanoparticles.
  • the process of encapsulating the semiconductor nanoparticles is carried out by slowly dropping or injecting a shell precursor solution for forming a shell layer into a semiconductor nanoparticle solution at a certain temperature to carry out a coating reaction.
  • the shell precursor solution may be formed by mixing a metal salt, a sulfur source, an organic complex, and a solvent.
  • the choice of sulfur source, the choice of organic complex and concentration, shell coating temperature, shell coating reaction time and dropping method have great influence on the luminescent properties, particle size, morphology and crystal structure of core-shell nanoparticles.
  • a process for encapsulating the surface of semiconductor nanoparticles with a zinc sulfide (ZnS) shell precursor solution has been reported to increase the fluorescence quantum yield of semiconductor nanoparticles.
  • ZnS zinc sulfide
  • Renguo Xie et al. use zinc stearate as the zinc salt, sulfur powder as the sulfur source, and oleylamine as the organic compound.
  • Compound, CuInS 2 /ZnS core-shell nanoparticles were synthesized at 180 °C.
  • the nanoparticle has a fluorescence quantum yield of up to 30%.
  • Thomas Pons et al. used zinc stearate as zinc salt, zinc hexyldithiocarbamate as sulfur source, trioctylphosphine and oleylamine as organic complexes, and synthesized C U InS 2 /ZnS core-shell nano
  • the quantum yield of particle fluorescence can reach up to 30% (Thomas Pons, et al., ACS Nano, 2010, 4 (5), 2531-2538).
  • Liang Li et al. used zinc stearate as a zinc salt and ethyl xanthate as a sulfur source, dissolved in a mixture of octadecene, dimethylformamide and toluene, and dripped the above mixed solution.
  • CuInS 2 /ZnS core-shell nanoparticles (Liang Li, et al "Chem. Mater. 2009, 21, 2422-2429 ) were obtained by adding CuInS 2 nanoparticle solution, and the fluorescence quantum yield can reach 60%, which is CuInS 2 10 times that of nanoparticles.
  • a method for preparing a core-shell nanoparticle solution comprises the following steps:
  • the semiconductor nanoparticle solution a) adjusting the semiconductor nanoparticle solution to a predetermined shell encapsulation temperature; b) adding a shell precursor solution to the semiconductor nanoparticle solution, and encapsulating the temperature at the predetermined shell The reaction is carried out, and the shell precursor solution is formed by mixing a component including a zinc salt, a mercapto mercaptan and a non-polar organic solvent;
  • the semiconductor is preferably selected from the group consisting of: ⁇ - ⁇ -VIA compounds or IIB-IB-IIIA-VIA compound.
  • the ⁇ - ⁇ -VIA compound, IB is preferably one or more of the following: Cu, Ag; ⁇ is preferably one or more of the following: In, Ga ; VIA is preferably selected from one or more of the following : Se, S.
  • the ⁇ - ⁇ -VIA compound is more preferably one of the following: CuInS 2 , AgInS 2 ,
  • the IB-IIIA-VIA compound is optimally selected from the group consisting of CuInS 2 , AgInS 2 , CuInSe 2 , AgInSe 2 , CuGaS 2 , CuInGaS, CuAglnS or AglnGaS.
  • the IIB-IB-IIIA-VIA compound, IB is preferably one or more of the following: Cu, Ag; ⁇ is preferably from one or more of the following: In, Ga ; VIA is preferably from the following one or A variety of: Se, S; Dai is selected from Zn.
  • the IIB-IB-IIIA-VIA compound is more preferably one of the following: ZnCuInS 2 , ZnAgInS 2 , ZnCuInSe 2 , ZnAgInSe 2 , ZnCuGaS 2 , ZnCuGaSe 2 , ZnAgGaS 2 , ZnAgGaSe 2 , ZnCuInGaS, ZnCuAglnS, ZnCuInGaSe, ZnCuAglnSe , ZnCuAglnSe , ZnAglnGaS, ZnCuAgGaS, ZnCuAgGaSe, ZnCuInSeS, ZnAglnSeS or ZnCuAgGaSeSo
  • the IIB-IB-IIIA-VIA compound is optimally selected from the group consisting of ZnCuInS 2 , ZnAgInS 2 , ZnCuInSe 2 , ZnAgInSe 2 or ZnAglnSeS.
  • the addition includes direct pouring or dropwise addition.
  • the shell precursor solution is formed by mixing a zinc salt, an alkyl mercaptan and a non-polar organic solvent, and heating until the zinc salt is dissolved.
  • organic complexes may optionally be added during the preparation of the shell precursor solution.
  • the organic complex is selected from one or more of the group consisting of phosphates and aliphatic amines.
  • the mercapto mercaptan has a molar content greater than the molar content of the zinc salt.
  • the molar ratio of the alkylthiol to the zinc salt is preferably (2 to 80): 1, more preferably (2 to 50): 1, most preferably (4 to 20): 1.
  • the zinc salt is selected from one or more of the following: zinc acetate, zinc chloride, zinc sulfate, zinc diethyldithiocarbamate, zinc dihexyldithiocarbamate, zinc stearate, oleic acid Zinc, zinc myristate, zinc palmitate, zinc laurate and zinc antimonate.
  • the mercapto mercaptan is selected from mercaptans bearing one or more mercapto functional groups.
  • the mercapto mercaptan is preferably one or more of the following: octyl mercaptan, isooctyl mercaptan, dodecyl mercaptan, tetradecyl mercaptan, hexadecanolyl mercaptan, eighteen Alkyl mercaptan, 1,8-dioctyl mercaptan and 1,6-dioctyl mercaptan.
  • the non-polar organic solvent is selected from one or more of the following: octadecene, dodecane, hexadecane, octadecyl, dimethylphenyl ether, hydrogenated terphenyl, paraffin, diphenyl ether, Dioctyl ether and dioxime ether.
  • the phosphate ester is selected from one or more of the following: trioctyl phosphate and tributyl phosphate.
  • the aliphatic amine is preferably one or more of the following: hexadecylamine, octadecylamine, tetradecylamine and oleylamine.
  • the molar ratio of the zinc salt to the phosphate is 1 : (1: 80), preferably 1 : (2: 50), more preferably 1: (4: 20).
  • the molar ratio of the zinc salt to the aliphatic group is 1 : (1: 80), preferably 1 : (2: 50), more preferably 1: (4: 20).
  • the shell coating temperature is from 150 ° C to 290 ° C, preferably from 200 ° C to 260 ° C, more preferably from 220 ° C to 250 ° C.
  • a method for preparing core-shell nano-particles comprises the following steps:
  • the core-shell nanoparticle solution prepared by any of the above methods is mixed with a polar solvent to form a suspension; and the suspension is separated to obtain the core-shell nanoparticles.
  • the polar solvent is selected from one or more of the following: methanol, ethanol, isopropanol, butanol, Methyl ethyl ketone and acetone.
  • the core composition of the core-shell nanoparticles differs depending on the semiconductor nanoparticles selected.
  • the shell component of the core-shell nanoparticles is ZnS.
  • the prepared core-shell nanoparticles can be represented as semiconductor nanoparticles/ZnS, for example, AgInS 2 /ZnS,
  • the surface of the core component of the core-shell nanoparticles may be partially or fully encapsulated by the shell component.
  • the core-shell nanoparticles prepared by the invention can be applied in the fields of light-emitting diodes, solar cells, lasers, electronic communication, anti-counterfeiting technology, biomarkers and the like.
  • mercapto mercaptan is used as an organic complex to chelate with a zinc salt to form a zinc organic compound during dissolution of the zinc salt, thereby improving the solubility of the zinc salt in a non-polar organic solvent.
  • mercapto mercaptan is also used as a sulfur source to slowly decompose and release sulfur at the shell coating temperature, and uniformly forms ZnS on the surface of the semiconductor nanoparticle with the above zinc organic compound, thereby reducing defects on the surface of the semiconductor nanoparticle crystal. , increase the fluorescence quantum yield of core-shell nanoparticles.
  • the slow decomposition of the alkyl mercaptan effectively avoids the nucleation of ZnS alone, reduces the formation of by-products, and further increases the fluorescence quantum yield of the core-shell nanoparticles.
  • the invention has the following characteristics:
  • the alkyl mercaptan used in the invention reduces defects on the surface of the semiconductor nanoparticle crystal, and also reduces the formation of by-products, thereby improving the fluorescence quantum yield of the core-shell nanoparticles, and obtaining the fluorescence quantum of the core-shell nanoparticles.
  • the yield can reach 75%.
  • the raw materials and reagents used in the present invention are inexpensive, readily available, non-toxic or low in toxicity, and low in production cost.
  • the invention adopts mercapto mercaptan as a sulfur source and an organic complex, which simplifies the kind of raw materials, can be simplified by a direct pouring process, is easy to control, has good reproducibility, and is easy to industrialize.
  • Figure 1 Ultraviolet-visible absorption spectrum of C U InS 2 /ZnS core-shell nanoparticles obtained according to an embodiment of the present invention.
  • Figure 2. Fluorescence of CuI n S 2 /ZnS core-shell nanoparticles obtained according to an embodiment of the present invention and
  • Figure 3. Transmission electron microscopy of C U InS 2 /ZnS core-shell nanoparticles prepared according to one embodiment of the present invention photo.
  • Figure 4 X-ray diffraction pattern of CuInS 2 nanoparticles and CuInS 2 /ZnS core-shell nanoparticles prepared in accordance with one embodiment of the present invention.
  • Adjusting the semiconductor nanoparticle solution to a predetermined shell encapsulation temperature adding the shell precursor solution (for example, can be directly poured) into the semiconductor nanoparticle solution, and pre-set the shell encapsulation temperature
  • the reaction is carried out. After the reaction is carried out for a predetermined reaction time, a core-shell nanoparticle solution of the semiconductor nanoparticles is obtained.
  • the core-shell nanoparticle solution is cooled to below the shell wrap temperature, such as room temperature.
  • the core-shell nanoparticle solution is mixed with a polar solvent to form a suspension, and the suspension is separated to obtain core-shell nanoparticles.
  • the manner in which the shell precursor solution is added to the semiconductor nanoparticle solution is preferably such that the two are mixed faster, such as by rapidly pouring the shell precursor solution into the semiconductor nanoparticle solution.
  • the semiconductor nanoparticles can be isolated from the prepared semiconductor nanoparticle solution, or can be prepared by other existing processes.
  • the semiconductor nanoparticle solution can be prepared by adding one or more of a metal salt, an indium salt, and a mercapto mercaptan, a carbon sulfide, a sulfur powder, a thiourea to a non-polar one.
  • an inert gas is introduced, and the mixture is heated to 200 ° ( ⁇ 290 ° C while stirring, and stirring is continued at this temperature for lm ! ⁇ 6 h to dissolve the metal salt, the indium salt and the alkyl mercaptan to obtain a semiconductor nanometer.
  • Particle solution The temperature and time during the preparation of the semiconductor nanoparticle solution will affect the particle size of the semiconductor nanoparticles, which in turn affects the luminescent properties of the core-shell nanoparticles.
  • the ratio of the total number of moles of the Group IB metal salt to the total moles of the lanthanide metal salt is from 1 to 2: 2 to 1, wherein the Group IB metal salt and the lanthanide metal salt may be optionally Proportional mixing; the molar content of the Group VIA element is greater than or equal to the total mole mole content of the Group IB and Group lanthanum metal salts.
  • the ratio of the total moles of the Group IB metal salt to the total moles of the lanthanum metal salt is 1-2: 2-1, the Group IB metal salt and the lanthanide metal salt may be optionally Proportional mixing; the molar content of the VIA group compound is greater than or equal to the total mole mole content of the IB group and the lanthanum metal salt, and the ratio of the total mole number of the lanthanum metal salt to the total number of moles of the Group IB and Group IIIA metal salts is 1-20: 20 ⁇ 1.
  • the Group IB metal salt is selected from one or more of the following: cuprous acetate, copper acetate, copper chloride, cuprous chloride, cuprous sulfate, cuprous nitrate, copper nitrate, cuprous iodide, stearic acid Cuprous acid, cuprous oleate, cuprous myristate, cuprous palmitate, cuprous laurate, cuprous bismuth, silver nitrate, silver sulphate, silver acetate or silver stearate.
  • the lanthanum metal salt is selected from one or more of the following: indium acetate, indium chloride, indium sulfate, indium nitrate, indium iodide, indium stearate, indium oleate, indium myristic acid, palmitic acid Indium, indium laurate, indium bismuth, gallium chloride, gallium sulfate, gallium stearate, gallium acetate or gallium nitrate.
  • the lanthanum metal salt is selected from one or more of the following: zinc acetate, zinc chloride, zinc sulfate, zinc diethyldithiocarbamate, zinc dihexyldithiocarbamate, zinc stearate, Zinc oleate, zinc myristate, zinc palmitate, zinc laurate and zinc antimonate.
  • the VIA group compound is selected from one or more of the following: selenium powder, bis(trimethylsilyl) selenium.
  • the mercapto mercaptan is preferably one or more of the following: octyl mercaptan, isooctyl mercaptan, dodecyl mercaptan, tetradecyl mercaptan, hexadecanolyl mercaptan, eighteen Mercaptothiol, 1,8-dioctyl mercaptan and 1,6-dioctyl mercaptan.
  • the non-polar organic solvent is selected from one or more of the following: octadecene, ruthenium, hexadecane, octadecyl, dimethylphenyl ether, hydrogenated terphenyl, paraffin, diphenyl ether, Dioctyl ether and dioxime ether.
  • the semiconductor nanoparticle solution can also be obtained by dispersing semiconductor nanoparticles into an organic solvent.
  • the organic solvent is selected from one or more of the following: octadecene, dodecane, hexadecane, octadecane, dimethylphenyl ether, hydrogenated terphenyl, paraffin, diphenyl ether, dioctyl ether And, oxime ether, thiol with one or more thiol functional groups, trioctyl phosphate, tributyl phosphate, hexadecylamine, octadecylamine, tetradecylamine and oleylamine.
  • the obtained core-shell nanoparticles were diluted with toluene and subjected to optical performance test.
  • the absorption spectra of the samples were tested using a UV-50 (Varian, USA) Violet visible spectrophotometer, and the same solution was subjected to fluorescence spectroscopy using a Cary Eclipse (Varian, USA) type spectrophotometer.
  • the PMT voltage was set to 600 V
  • the excitation wavelength was 485 nm
  • the excitation and emission slit widths were both 5.0 nm.
  • the absorbance of the core-shell nanoparticles at a wavelength of 485 nm is about 0.05, thereby avoiding the influence of sample re-absorption on the subsequent data calculation process.
  • the fluorescence quantum yield of the core-shell nanoparticles was determined using a rhodamine B ethanol solution (the quantum yield of rhodamine B in an ethanol solution of 97%) as a standard. During the test, the ethanol solution of Rhodamine B was adjusted to the absorbance of the core-shell nanoparticles at the excitation wavelength, and was controlled at about 0.05 to avoid reabsorption of the sample. The integrated area of the fluorescence peak was calculated based on the obtained fluorescence spectrum, and the fluorescence quantum yield of the core-shell nanoparticles was calculated by the formula. YQ is the quantum yield of the core-shell nanoparticles to be tested,
  • Y S is the fluorescence quantum yield of the standard dye Rhodamine B in ethanol solution
  • F Q and Fs are the integrated fluorescence intensities of the core-shell nanoparticles toluene solution and rhodamine B ethanol solution to be tested.
  • 0 (3 and 0 5 are the refractive indices of the toluene solvent used to dilute the core-shell nanoparticles and the ethanol solvent used to dilute the rhodamine B, respectively.
  • the core-shell nanoparticle toluene solution was dropped on the glass and naturally dried to form a film.
  • the composition of the core-shell nanoparticles was tested by an X-ray diffractometer (Nippon Science, D/max-2200/PC). Using Cu/ ⁇ - ⁇ as the radiation source, the operating voltage is 40 KV, the current is 30 mA, the scanning range is 20-70 °, and the scanning rate is 6 min.
  • the copper mesh is immersed in the cleaned core-shell nanoparticle toluene solution, and is naturally dried.
  • Example 1 Effect of Shell Wrap Time on CuInS 2 /ZnS Core-shell Nanoparticles Properties 0.293 g of zinc acetate, 3 ml of dodecanethiol and 6 ml of octadecene solvent were mixed. The mixture was heated to 100 ° C until the zinc salt dissolved to form a shell precursor solution.
  • the shell precursor solution was quickly poured into the CuInS 2 nanoparticle solution, and reacted at a shell coating temperature of 240 ° C for a predetermined reaction time (see Table 1) to obtain a CuInS 2 /ZnS core-shell nanoparticle.
  • the solution was cooled to room temperature.
  • Figure 1 and Figure 2 show the UV-visible absorption spectra and fluorescence spectra of core-shell nanoparticle samples Yl, Y3, Y5, Y6, Y8-10, and sample Y16, respectively.
  • 3 is a transmission electron micrograph of a core-shell nanoparticle sample Y7.
  • the fluorescence spectrum wavelength of CuInS 2 /ZnS core-shell nanoparticles can be adjusted by controlling the stirring time during the preparation of C U InS 2 nanoparticle solution and the reaction time of encapsulation reaction, and the luminescence of different colors can be obtained. After optimization of the process conditions, orange light with a fluorescence spectrum wavelength of 589 nm can be obtained, and the fluorescence quantum yield can reach 75%.
  • Example 2 Effect of the amount of zinc salt on the properties of CuInS 2 /ZnS core-shell nanoparticles Mix a certain amount of zinc acetate (see Table 2), 3 ml of dodecyl mercaptan and 6 ml of octadecene solvent. The mixture was heated to 100 ° C until the zinc salt dissolved to form a shell precursor solution.
  • the shell precursor solution was quickly poured into a CuInS ⁇ ft rice particle solution, and reacted at 220 ° C for a predetermined reaction time (see Table 2) to obtain a solution containing CuInS 2 /ZnS core-shell nanoparticles, and Cool to room temperature.
  • Example 3 Effect of Stirring Temperature on Properties of CuInS 2 /ZnS Core-Shell Nanoparticles 0.440 g of zinc acetate, 3 ml of 1-dodecanethiol and 6 ml of octadecene solvent were mixed. The mixture was heated to 100 ° C until the zinc salt dissolved to form a shell precursor solution.
  • cuprous acetate 0.175 g of cuprous acetate, 0.175 g of indium acetate and 1.50 ml of dodecanethiol were added to 15.00 ml of octadecene solvent, and degassed under a nitrogen atmosphere for 30 min, and then stirred at 260 ° C for 30 min to form CuInS 2 nm.
  • the particle solution was cooled to 240 °C.
  • the shell precursor solution was quickly poured into the CuInS 2 nanoparticle solution, and reacted at 240 ° C for a predetermined reaction time (see Table 3) to obtain a solution containing CuInS 2 /ZnS core-shell nanoparticles, which was cooled. To room temperature.
  • the precipitate was dispersed in toluene, and a mixed solution of acetone and isopropyl alcohol (volume ratio of acetone and isopropanol of 4:1) in a volume of 3 times of toluene was added thereto, followed by centrifugal sedimentation, and the above procedure was repeated twice.
  • the obtained C U InS 2 /ZnS core-shell nanoparticles were dispersed in toluene and stored under a nitrogen atmosphere.
  • Table 3 shows the preparation conditions and properties of C U InS 2 /ZnS core-shell nanoparticles.
  • Example 4 Variation of non-polar organic solvent The properties of C U InS 2 /ZnS core-shell nanoparticles were mixed with 0.440 g of zinc acetate, 3 ml of dodecyl mercaptan and 6 ml of octadecene solvent. Mixture Heat to 100 ° C until the zinc salt dissolves to form a shell precursor solution.
  • cuprous acetate 0.175 g of indium acetate and 1.50 ml of dodecanethiol were added to 15 ml of xylyl ether, and the mixture was degassed under a nitrogen atmosphere for 30 min, and then stirred at 240 ° C for 60 min to form CuInS 2 nanoparticles. The solution was cooled to 220 °C.
  • the shell precursor solution is quickly poured into the CuInS 2 nanoparticle solution and reacted at 220 ° C.
  • the precipitate was dispersed in toluene, and a mixed solution of acetone and isopropyl alcohol in a volume of 3 times of toluene was added.
  • the shell precursor solution was quickly poured into a CuInS 2 nanoparticle solution, and after reacting at 220 ° C for 120 min, a solution containing CuInS 2 /ZnS core-shell nanoparticles was obtained, and it was cooled to room temperature.
  • the obtained CuInS 2 /Z n S core-shell nanoparticles were dispersed in toluene and stored under a nitrogen atmosphere.
  • the CuInS 2 /ZnS core-shell nanoparticles formed had a fluorescence quantum yield of 53.7% and a fluorescence spectrum wavelength of 605 nm.
  • Example 6 Effect of organic complex oleylamine on C U InS 2 /ZnS core-shell nanoparticles Properties 0.2205 g of zinc acetate, 3 ml of dodecyl mercaptan, 3 ml of oleylamine and 6 ml of octadecene solvent were mixed. The mixture is heated to 10 (TC until the zinc salt dissolves to form a shell precursor solution.
  • the shell precursor solution was quickly poured into a CuInS 2 nanoparticle solution, and after reacting at 240 ° C for 60 min, a solution containing CuInS 2 /ZnS core-shell nanoparticles was obtained, and it was cooled to room temperature.
  • the precipitate was dispersed in toluene, and a mixed solution of acetone and isopropyl alcohol (volume ratio of acetone and isopropanol of 4:1) in a volume of 3 times of toluene was added thereto, followed by centrifugal sedimentation, and the above procedure was repeated twice.
  • the obtained C U InS 2 /ZnS core-shell nanoparticles were dispersed in toluene and stored under a nitrogen atmosphere.
  • the CuInS 2 /ZnS core-shell nanoparticles formed had a fluorescence quantum yield of 20.9% and a fluorescence spectrum wavelength of 576 nm.
  • Example 7 Effect of organic complex octadecylamine on C U InS 2 /ZnS core-shell nanoparticles Properties 0.2205 g of zinc acetate, 3 ml of dodecyl mercaptan, 3 ml of octadecylamine and 6 ml of octadecene solvent were mixed. The mixture was heated to 100 ° C until the zinc salt dissolved to form a shell precursor solution.
  • the shell precursor solution is quickly poured into the CuInS 2 nanoparticle solution and reacted at 240 ° C. After 60 min, a solution containing CuInS 2 /ZnS core-shell nanoparticles was obtained and cooled to room temperature. Adding a solution containing CuInS 2 /ZnS core-shell nanoparticles in 4 volumes of a mixed solution of acetone and isopropanol (volume ratio of acetone to isopropanol of 4:1) to form a suspension, and centrifuging the suspension to remove centrifugal sedimentation After the upper layer solution, a C U InS 2 /ZnS core-shell nanoparticle precipitate was obtained.
  • the precipitate was dispersed in toluene, and a mixed solution of acetone and isopropyl alcohol in a volume of 3 times of toluene was added.
  • Example 8 Effect of organic complex trioctyl phosphate on properties of C U InS 2 /Z n S core-shell nanoparticles
  • a mixture of 0.2205 g of zinc acetate, 3 ml of dodecyl mercaptan, 5 ml of trioctyl phosphate and 3 ml of octadecene solvent was mixed. The mixture was heated to 100 ° C until the zinc salt dissolved to form a shell precursor solution.
  • the shell precursor solution was quickly poured into a CuInS 2 nanoparticle solution, and after reacting at 230 ° C for 60 min, a solution containing CuInS 2 /ZnS core-shell nanoparticles was obtained, which was cooled to room temperature.
  • the shell precursor solution was quickly poured into the AgInS 2 nanoparticle solution, and after reacting at 220 ° C for 60 min, a solution containing AgInS 2 /ZnS core-shell nanoparticles was obtained, which was cooled to room temperature.
  • Example 10 Synthesis of ZnCuInS 2 /ZnS core-shell nanoparticles
  • the shell precursor solution was quickly poured into a ZnCuInS 2 nanoparticle solution, and after reacting at 220 Torr for 60 min, a solution containing ZnCuInS 2 /ZnS core-shell nanoparticles was obtained, which was cooled to room temperature.
  • the 0111 ⁇ 2 nanoparticles were dispersed in 5 ml of toluene, washed with 20 ml of acetone, and then sedimented by centrifugation, and the above procedure was repeated twice.
  • the obtained CuInS 2 nanoparticles were dispersed in 11 ml of octadecene, and after degassing for 30 min under a nitrogen atmosphere, the temperature was rapidly raised to 240 ° C, and the shell precursor solution was quickly poured into the shell precursor solution, and after heating for 60 min, CuInS 2 was obtained.
  • a solution of /ZnS core-shell nanoparticles was cooled to room temperature.
  • the precipitate was dispersed in toluene, and a mixed solution of acetone and isopropyl alcohol (volume ratio of acetone to isopropanol of 4:1) in a volume of 3 times of toluene was added thereto, followed by centrifugation, and the above procedure was repeated twice.
  • the obtained CuInS ZnS core-shell nanoparticles were dispersed in toluene and stored under a nitrogen atmosphere.
  • the formed CuInS 2 /ZnS core-shell nanoparticles have a fluorescence quantum yield of 70% and a fluorescence spectrum wavelength of 561 nm.

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Abstract

提供一种制备核壳纳米粒子及其溶液的方法。所述核壳纳米粒子溶液的制备方法包括如下步骤：将半导体纳米粒子溶液调节至一预设定的壳层包裹温度；将一壳层前驱体溶液加入到所述半导体纳米粒子溶液中，并在所述预设定的壳层包裹温度下进行反应，所述壳层前驱体溶液由包括锌盐、烷基硫醇和非极性有机溶剂的成分混合形成；在所述反应进行一预设定反应时间后，得到所述半导体纳米粒子的核壳纳米粒子溶液。得到的核壳纳米粒子具有荧光量子产率高、无毒、生产成本低，工艺简单的优点。

Description

一种制备核壳纳米粒子及其溶液的方法 技术领域
本发明涉及一种制备核壳纳米粒子及其溶液的方法。 背景技术
无机半导体纳米粒子具有性能稳定、 激发光谱宽、 荧光光谱窄、 发 光性能受周围环境影响小等特点， 能够有效的代替有机发光材料， 在太 阳能电池、 发光二极管、 荧光探针、 生物标记、 防伪标记、 功能薄膜、 激光、 电子通信等领域得到广泛的应用。
大多数无机半导体纳米粒子由于含有镉、 砷、 铅、 硒等元素， 具有 较高毒性， 会对环境造成污染， 不利于商业化应用。 因而， 无毒或低毒、 太阳光吸收系数高、 光稳定性高的半导体纳米粒子得到了广泛的研究， 如 IB-IIIA-VIA族纳米粒子或 IIB-IB-IIIA-VIA族纳米粒子等。
然而， 这些半导体纳米粒子在制备过程中产生的晶体表面缺陷以及 副产物， 都会成为荧光淬灭中心， 而降低半导体纳米粒子的荧光量子产 率。 研究发现， 使用宽禁带的无机半导体材料对半导体纳米粒子进行包 裹以形成一种核壳纳米粒子， 可以有效降低晶体表面的缺陷， 提高半导 体纳米粒子的荧光量子产率， 增强光稳定性。
通常， 对半导体纳米粒子进行包裹的工艺是在一定温度下， 将用于 形成壳层的壳层前驱体溶液缓慢滴加或注入半导体纳米粒子溶液中， 进 行包裹反应。 壳层前驱体溶液可以由金属盐、 硫源、 有机配合物和溶剂 等混合形成。 硫源的选择、 有机配合物的选择及浓度、 壳层包裹温度、 壳层包裹反应时间和滴加方式对核壳纳米粒子的发光性能、 颗粒尺寸、 形貌、 晶体结构有较大影响。
己有报道描述用硫化锌 （ZnS ) 壳层前驱体溶液在半导体纳米粒子 表面进行包裹的工艺， 旨在提高半导体纳米粒子的荧光量子产率。例如， Renguo Xie等采用硬脂酸锌作为锌盐， 硫粉作为硫源， 油胺作为有机配 合物， 在 180°C合成了 CuInS2/ZnS核壳纳米粒子。 该纳米粒子的荧光量 子产率最高可达到 30%。他们还采用相同的方法制备了 AgInS2/ZnS核壳 纳米粒子 (Renguo Xie, et al., JACS, 2009， 131, 5691-5697 )。
又如， Thomas Pons等采用硬脂酸锌作为锌盐、 双己基二硫代氨基 甲酸锌作为硫源， 三辛基膦和油胺作为有机配合物， 合成的 CUInS2/ZnS 核壳纳米粒子荧光量子产率最高可以达到 30% ( Thomas Pons, et al., ACS Nano, 2010, 4 (5), 2531-2538 )。
再如， Liang Li等将硬脂酸锌作为锌盐、 乙基黄原酸锌作为硫源， 溶于十八烯、 二甲基甲酰胺和甲苯的混合液中， 并将上述混合溶液逐滴 加入 CuInS2纳米粒子溶液中， 得到 CuInS2/ZnS核壳纳米粒子（Liang Li, et al" Chem. Mater. 2009, 21, 2422-2429 ) , 其荧光量子产率可以达到 60%, 是 CuInS2纳米粒子的 10倍。
还有， Victor I. Klimov 课题组将硬脂酸锌或油酸镉作为锌盐或镉 盐、 硫粉作为硫源， 三辛基膦为配合物， 溶解于十八烯中， 在 210°C下 逐滴加入 CuInS2纳米粒子溶液中， 得到 CuInS2/ZnS 核壳纳米粒子或 CuInS2/CdS 核壳纳米粒子， 其最高量子产率分别可达到 67%或 86% (Liang Li, et al., JACS, 2011, 133(5), 1176-1179)。 发明内容
根据本发明的一个实施例， 本发明所提供的一种制备核壳纳米粒子 溶液的方法， 包括以下步骤：
a) 将半导体纳米粒子溶液调节至一预设定的壳层包裹温度； b) 将一壳层前驱体溶液加入到所述半导体纳米粒子溶液中， 并在所 述预设定的壳层包裹温度下进行反应，所述壳层前驱体溶液由包括锌盐、 垸基硫醇和非极性有机溶剂的成分混合形成；
c)在所述反应进行一预设定反应时间后， 得到所述半导体纳米粒子 的核壳纳米粒子溶液；
所述半导体优选自下面的一种： ΙΒ-ΙΠΑ-VIA 族化合物或 IIB-IB-IIIA-VIA族化合物。
所述 ΙΒ-ΙΠΑ-VIA族化合物， IB优选自下面的一种或多种： Cu、 Ag; ΙΠΑ优选自下面的一种或多种： In、 Ga; VIA优选自下面的一种或多种： Se、 S。
所述 ΙΒ-ΙΠΑ-VIA族化合物更优选自下面的一种： CuInS2、 AgInS2、
CuInSe2、 AgInSe2、 CuGaS2、 CuGaSe2、 AgGaS2、 AgGaSe2、 CuInGaS、 CuAgInS、 CuInGaSe、 CuAgInSe、 AgInGaS、 AgInGaSe、 CuAgGaS、 CuAgGaSe、 CuInSeS、 AglnSeS或 CuAgGaSeS。
所述 IB-IIIA-VIA族化合物最优选自下面的一种： CuInS2、 AgInS2、 CuInSe2、 AgInSe2、 CuGaS2、 CuInGaS、 CuAglnS或 AglnGaS。
所述 IIB-IB-IIIA-VIA族化合物， IB优选自下面的一种或多钟： Cu、 Ag; ΙΠΑ优选自下面的一种或多种： In、 Ga; VIA优选自下面的一种或 多种： Se、 S; ΠΒ族选自 Zn。
所述 IIB-IB-IIIA-VIA 族化合物更优选自下面的一种： ZnCuInS2、 ZnAgInS2、 ZnCuInSe2、 ZnAgInSe2、 ZnCuGaS2、 ZnCuGaSe2、 ZnAgGaS2、 ZnAgGaSe2、 ZnCuInGaS、 ZnCuAglnS、 ZnCuInGaSe、 ZnCuAglnSe、 ZnAglnGaS、 ZnAglnGaSe、 ZnCuAgGaS、 ZnCuAgGaSe、 ZnCuInSeS、 ZnAglnSeS 或 ZnCuAgGaSeSo
所述 IIB-IB-IIIA-VIA族化合物最优选自下面的一种： ZnCuInS2、 ZnAgInS2、 ZnCuInSe2、 ZnAgInSe2或 ZnAglnSeS。
所述加入包括直接倒入或逐滴滴加。
所述壳层前驱体溶液是由锌盐、 烷基硫醇和非极性有机溶剂混合、 加热直至锌盐溶解而形成的。
所述壳层前驱体溶液制备过程中可选的加入其它有机配合物。 所述 有机配合物选自下面的一种或多种： 磷酸酯和脂肪族胺。
所述垸基硫醇的摩尔含量大于锌盐摩尔含量。
所述烷基硫醇与锌盐的摩尔比优选为 (2〜80) : 1 ,更优选为 （2~50) ： 1， 最优选为 （4~20) ： 1。 所述锌盐选自下面的一种或多种： 醋酸锌、 氯化锌、 硫酸锌、 二乙 基二硫代氨基甲酸锌、 二己基二硫代氨基甲酸锌、 硬脂酸锌、 油酸锌、 肉豆蔻酸锌、 棕榈酸锌、 月桂酸锌和癸酸锌。
所述垸基硫醇选自带有一个或者一个以上巯基官能团的硫醇。
所述垸基硫醇优选自下面的一种或多种： 辛基硫醇、 异辛基硫醇、 十二垸基硫醇、 十四垸基硫醇、 十六垸基硫醇、 十八烷基硫醇、 1,8-二辛 基硫醇和 1,6-二辛基硫醇。
所述非极性有机溶剂选自下面的一种或多种： 十八烯、 十二烷、 十 六垸、 十八垸、 二甲基苯基醚、 氢化三联苯、 石蜡、 二苯醚， 二辛醚和 二卞醚。
所述磷酸酯选自下面的一种或多种： 磷酸三辛脂和磷酸三丁酯。 所述脂肪族胺优选自下面的一种或多种： 十六胺、 十八胺、 十四胺 和油胺。
所述锌盐与磷酸酯的摩尔比为 1 :(1： 80)， 优选为 1 :(2： 50), 更优选 为 1 :(4： 20)。
所述锌盐与脂肪族的摩尔比为 1 :(1： 80), 优选为 1 :(2： 50), 更优选 为 1 :(4： 20)。
所述壳层包裹温度是 150°C〜290°C， 优选 200°C~260°C， 更优选 220°C〜250°C。
所述反应时间是 lmir！〜 4h， 优选 5min〜3h， 更优选 15min〜2h。 根据本发明的另一个实施例， 本发明所提供的一种制备核壳纳米粒 子的方法， 包括以下步骤：
将上述任意一种方法制备的核壳纳米粒子溶液与一极性溶剂混合形 成悬浮液； 分离所述悬浮液得到所述核壳纳米粒子。
进一步包括步骤： 将所述分离得到的核壳纳米粒子进行至少一次清 洗， 以去除杂质。
所述极性溶剂选自下面的一种或多种： 甲醇、 乙醇、 异丙醇、 丁醇、 甲乙酮和丙酮。
所述核壳纳米粒子的核组分根据所选用的半导体纳米粒子的不同而 不同。 所述核壳纳米粒子的壳层组分为 ZnS。 相应的， 所制备的核壳纳 米粒子可以表示为半导体纳米粒子 /ZnS， 例如、 AgInS2/ZnS、
AgCuInS2/ZnS、 ZnCuInS2/ZnS和 ZnAgInS2/ZnS等。 核壳纳米粒子的核 组分表面可以部分或全部被壳层组分包裹。
本发明制备得到的核壳纳米粒子可以应用在发光二极管、 太阳能电 池、 激光、 电子通信、 防伪技术、 生物标记等领域。
在本发明中， 垸基硫醇一方面作为有机配合物， 在锌盐溶解过程中 与锌盐螯合形成锌有机化合物， 提高了锌盐在非极性有机溶剂中的溶解 性。 另一方面， 垸基硫醇也作为硫源， 在壳层包裹温度下缓慢分解释放 出硫， 并与上述锌有机化合物在半导体纳米粒子表面均匀生成 ZnS， 从 而降低了半导体纳米粒子晶体表面的缺陷， 提高核壳纳米粒子的荧光量 子产率。 进一步， 烷基硫醇的缓慢分解有效避免了 ZnS单独成核， 降低 了副产物的生成， 进一步提高了核壳纳米粒子的荧光量子产率。
本发明与现有技术相比具有以下特点：
1.本发明采用的烷基硫醇降低了半导体纳米粒子晶体表面的缺陷， 也降低了副产物的生成， 从而提高了核壳纳米粒子的荧光量子产率， 得 到的核壳纳米粒子的荧光量子产率可以达到 75%。
2. 本发明采用的原料和试剂价格低廉、 容易得到、 无毒或低毒、 生 产成本低。
3. 本发明采用垸基硫醇作为硫源和有机配合物， 简化了原料种类、 可采用直接倒入工艺简化工艺过程、 过程容易控制、 再现性好， 易于工 业化。 附图说明
图 1. 根据本发明的实施例得到的 CUInS2/ZnS核壳纳米粒子的紫外可见 吸收光谱。 图 2. 根据本发明的实施例得到的 CuInS2/ZnS 核壳纳米粒子的荧光光 並 图 3. 根据本发明的一个实施例制备的 CUInS2/ZnS核壳纳米粒子的透射 电镜照片。
图 4. 根据本发明的一个实施例制备的 CuInS2纳米粒子和 CuInS2/ZnS核 壳纳米粒子的 X射线衍射图。
图 5. 根据本发明的一个实施例制备的 CuInS2纳米粒子的透射电镜照 片。
所列附图用于进一步描述利用本发明的公开的具体实施例和方法， 附图以及该描述是示例性而非限制性的。 具体实施方式
下面结合具体实施例， 进一步阐述本发明。 应理解， 这些实施例仅 用于说明本发明而不用于限制本发明的范围。 此外应理解， 在阅读了本 发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改， 这些等价形式同样落于本申请所附权利要求书所限定的范围。
将半导体纳米粒子溶液调节至预设定的壳层包裹温度， 将壳层前驱 体溶液加入.（例如可以直接倒入） 到所述半导体纳米粒子溶液中， 并在 预设定的壳层包裹温度下进行反应。 反应进行一预设定反应时间后， 得 到半导体纳米粒子的核壳纳米粒子溶液。 将所述核壳纳米粒子溶液冷却 至所述壳层包裹温度以下， 例如室温。 将上述核壳纳米粒子溶液与一极 性溶剂混合形成悬浮液， 分离上述悬浮液得到核壳纳米粒子。 将壳层前 驱体溶液加入到半导体纳米粒子溶液中的方式优选能较快使两者较快混 合的方式，例如快速的将壳层前驱体溶液倾倒入半导体纳米粒子溶液中。
半导体纳米粒子可以从制备的半导体纳米粒子溶液中分离得到， 也 可以采用其他现有工艺制备得到。
例如：所述半导体纳米粒子溶液可以采用如下步骤制备：将金属盐、 铟盐和垸基硫醇、 硫化碳、 硫粉、 硫脲中的一种或多种加入到非极性有 机溶剂中， 通入惰性气体， 边搅拌边加热至 200° (〜 290°C， 并在此温度 下继续搅拌 lm ！〜 6h， 使金属盐、 铟盐和烷基硫醇溶解， 得到半导体纳 米粒子溶液。 制备半导体纳米粒子溶液过程中的温度和时间将影响半导 体纳米粒子的粒径大小， 进而影响核壳纳米粒子的发光性能。
在 ΙΒ-ΠΙΑ-VIA族化合物半导体溶液中， IB族金属盐总摩尔数与 ΠΙΑ 族金属盐总摩尔数的比例为 1〜2： 2〜1， 其中 IB族金属盐与 ΠΙΑ族金属 盐可以任意比例混合； VIA族元素的摩尔含量大于或等于 IB族和 ΙΠΑ 族金属盐总摩尔数摩尔含量。
在 IIB-IB-IIIA-VIA族化合物半导体溶液中， IB族金属盐总摩尔数 与 ΙΠΑ族金属盐总摩尔数的比例 1~2： 2-1 , IB族金属盐与 ΠΙΑ族金属 盐可以任意比例混合； VIA族化合物的摩尔含量大于或等于 IB族和 ΠΙΑ 族金属盐总摩尔数摩尔含量， ΠΒ族金属盐总摩尔数与 IB族和 IIIA族金 属盐摩尔总数的比例为 1~20： 20〜1。
所述 IB族金属盐选自下面的一种或多种： 醋酸亚铜、 醋酸铜、 氯化 铜、 氯化亚铜、 硫酸亚铜、 硝酸亚铜、 硝酸铜、 碘化亚铜、 硬脂酸亚铜、 油酸亚铜、 肉豆蔻酸亚铜、 棕榈酸亚铜、 月桂酸亚铜、 癸酸亚铜、 硝酸 银、 硫酸银、 醋酸银或硬脂酸银。
所述的 ΙΠΑ族金属盐选自下面的一种或多种： 醋酸铟、 氯化铟、 硫 酸铟、 硝酸铟、 碘化铟、 硬脂酸铟、 油酸铟、 肉豆蔻酸铟、 棕榈酸铟、 月桂酸铟、 癸酸铟、 氯化镓、 硫酸镓、 硬脂酸镓、 醋酸镓或硝酸镓。
所述 ΠΒ族金属盐选自下面的一种或多种： 醋酸锌、 氯化锌、 硫酸 锌、 二乙基二硫代氨基甲酸锌、 二己基二硫代氨基甲酸锌、 硬脂酸锌、 油酸锌、 肉豆蔻酸锌、 棕榈酸锌、 月桂酸锌和癸酸锌。
所述 VIA族化合物选自下面的一种或多种： 硒粉、二（三甲基硅基） 硒。
所述垸基硫醇优选自下面的一种或多种： 辛基硫醇、 异辛基硫醇、 十二垸基硫醇、 十四垸基硫醇、 十六垸基硫醇、 十八.焼基硫醇、 1,8-二辛 基硫醇和 1,6-二辛基硫醇。 所述非极性有机溶剂选自下面的一种或多种： 十八烯、 十二垸、 十 六垸、 十八垸、 二甲基苯基醚、 氢化三联苯、 石蜡、 二苯醚， 二辛醚和 二卞醚。
所述半导体纳米粒子溶液， 也可以采用将半导体纳米粒子分散至有 机溶剂得到。
所述有机溶剂选自下面的一种或多种： 十八烯、 十二烷、 十六烷、 十八烷、 二甲基苯基醚、 氢化三联苯、 石蜡、 二苯醚， 二辛醚和、 卞醚、 带有一个或者一个以上巯基官能团的硫醇、 磷酸三辛脂、 磷酸三丁酯、 十六胺、 十八胺、 十四胺和油胺。
下列实施例中未注明具体条件的实验方法， 通常按照常规条件， 如 催化剂化学操作手册， 或按照制造厂商所建议的条件。
核壳纳米粒子的表征方法如下：
1) 紫外可见吸收光谱与荧光光谱
对获得的核壳纳米粒子用甲苯稀释后进行光学性能测试。 采用 UV-50 (Varian，USA)紫夕卜可见分光光度计测试样品的吸收光谱， 对相同 的溶液采用 Cary Eclipse (Varian,USA) 型荧光分光光度计进行荧光光谱 测试。 测量荧光光谱时， PMT 电压设置为 600 V， 激发波长为 485nm， 激发和发射狭缝宽度均为 5.0 nm。对核壳纳米粒子用甲苯稀释时， 要使核壳 纳米粒子在波长为 485nm处的吸光度在 0.05左右， 从而避免样品的重吸收 对后续数据计算过程的影响。
2) 荧光量子产率
以罗丹明 B乙醇溶液 （罗丹明 B在乙醇溶液的量子产率为 97%) 作为 标准测定核壳纳米粒子的荧光量子产率。测试时将罗丹明 B的乙醇溶液与核 壳纳米粒子在激发波长处的吸光度调成一致， 且控制在 0.05 左右以避免样 品的重吸收。基于获得的荧光光谱计算荧光峰的积分面积， 并通过公式计算 核壳纳米粒子的荧光量子产率。
Figure imgf000010_0001
YQ为待测核壳纳米粒子的量子产率，
YS为标准染料罗丹明 B在乙醇溶液的荧光量子产率，
FQ 、 Fs为待测核壳纳米粒子甲苯溶液、罗丹明 B乙醇溶液的积分荧光 强度，
八(3与 As 分别为待测核壳纳米粒子甲苯溶液与罗丹明 B乙醇溶液在激 发波长处的吸光度， 和
0(3与05分别为用于稀释核壳纳米粒子的甲苯溶剂与用于稀释罗丹明 B 的乙醇溶剂的折射系数。
3) X射线衍射 （XRD)
将核壳纳米粒子甲苯溶液滴于玻璃上， 自然晾干后形成薄膜。 利用 X 射线衍射仪 （日本理学株式会社， D/max-2200/PC) 对核壳纳米粒子的成分 进行测试。 采用 Cu/Κ-α为射线源， 操作电压为 40 KV, 电流为 30 mA， 扫 描范围为 20-70 °， 扫描速率为 6 min。
4)透射电镜 （TEM)
将铜网浸渍于清洗后的核壳纳米粒子甲苯溶液中， 自然风干后采用
TEM, Philips CM 20型场发射透射电镜获得样品的透射电镜照片。 实施例 1 : 壳层包裹时间对 CuInS2/ZnS核壳纳米粒子性能影响 混合 0.293g醋酸锌、 3ml十二硫醇和 6ml十八烯溶剂。 将混合物加 热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.051g醋酸亚铜， 0.120g醋酸铟和 1.03ml 十二硫醇加入到 10.3ml 十八烯溶剂中， 在氮气气氛下搅拌脱气 30min后， 在 240°C下搅拌一定时 间 （见表 1 ) ， 形成 CuInS2纳米粒子溶液。
将壳层前驱体溶液快速倒入 CuInS2纳米粒子溶液，在 240°C的壳层包裹 温度下反应一预设定反应时间（见表 1 )后， 得到含有 CuInS2/ZnS核壳纳米 粒子的溶液， 并将其冷却至室温。
加入含有 CuInS2/ZnS核壳纳米粒子的溶液 3倍体积的丙酮和异丙醇混 合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 CUInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，然后加入甲苯 3倍体积的丙酮和异丙醇混合溶 液（丙酮与异丙醇体积比为 4: 1 )进行清洗， 再离心沉降， 重复上述过程 2 次。 得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 表 1是 CUInS2/ZnS核壳纳米粒子制备条件及其性能。 图 1和图 2分别是核 壳纳米粒子样品 Yl， Y3 , Y5 , Y6, Y8-10, 以及样品 Y16的紫外可见 吸收光谱和荧光光谱。 图 3是核壳纳米粒子样品 Y7的透射电镜照片。
表 1 : CuInS2/ZnS核壳纳米粒子制备条件及其性倉 I
Figure imgf000012_0001
实验表明， 通过控制制备 CUInS2纳米粒子溶液过程中的搅拌时间和 进行包裹反应的反应时间， 可以调节 CuInS2/ZnS核壳纳米粒子的荧光光 谱波长， 得到不同颜色的发光。 经过工艺条件优化， 可以得到荧光光谱 波长为 589nm的橙色光， 其荧光量子产率可以达到 75%。 实施例 2: 锌盐用量对 CuInS2/ZnS核壳纳米粒子性能影响 混合一定量的醋酸锌 （见表 2 ) 、 3ml十二硫醇和 6ml十八烯溶剂。 将混合物加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.036g醋酸亚铜， 0.084g醋酸铟和 0.72ml十二硫醇加入到 7.20ml 十八烯溶剂中，在氮气气氛下搅拌脱气 30min后，在 240°C下搅拌 60min， 形成 CuInS ft米粒子溶液， 并将其冷却至 220°C。
将壳层前驱溶液快速倒入 CuInS^ft米粒子溶液，在 220°C下反应一预设 定反应时间 （见表 2)后， 得到含有 CuInS2/ZnS核壳纳米粒子的溶液， 并将 其冷却至室温。
加入是含有 CuInS2/ZnS核壳纳米粒子的溶液 3倍体积的丙酮和异丙醇 混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 CUInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶液 (丙酮和异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过程 2 次。 将得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 表 2是 CuInS2/ZnS核壳纳米粒子制备条件及其性能。 图 4是核壳纳米粒子 样品 Yl l， Y13和 Υ5的 XRD光谱。 图 5是核壳纳米粒子样品 Yl 1的 透射电镜照片。
表 2: CuInS2/ZnS核壳纳米粒子制备条件及其性會 I
Figure imgf000013_0001
实施例 3 : 搅拌温度对 CuInS2/ZnS核壳纳米粒子性能影响 混合 0.440g醋酸锌、 3ml 1-十二碳硫醇和 6ml十八烯溶剂。 将混合 物加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.075g醋酸亚铜， 0.175g醋酸铟和 1.50ml十二硫醇加入到 15.00ml 十八烯溶剂中，在氮气气氛下搅拌脱气 30min后，在 260°C下搅拌 30min， 形成 CuInS2纳米粒子溶液， 并将其冷却至 240°C。
将壳层前驱体溶液快速倒入 CuInS2纳米粒子溶液，在 240°C下反应一预 设定反应时间 （见表 3 )后， 得到含有 CuInS2/ZnS核壳纳米粒子的溶液， 将 其冷却至室温。
加入是含有 CuInS2/ZnS核壳纳米粒子的溶液 3倍体积的丙酮和异丙醇 混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 CuInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶液 (丙酮和异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过程 2 次。 将得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 表 3是 CUInS2/ZnS核壳纳米粒子制备条件及其性能。
表 3 : CuInS2/ZnS核壳纳米粒子制备条件及其性肯
Figure imgf000014_0001
实施例 4: 非极性有机溶剂变化对 CUInS2/ZnS核壳纳米粒子性能影 混合 0.440g醋酸锌、 3ml 十二硫醇和 6ml 十八烯溶剂。 将混合物 加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.074g醋酸亚铜， 0.175g醋酸铟和 1.50ml 十二硫醇加入到 15ml 二甲苯基醚中，在氮气气氛下搅拌脱气 30min后，在 240°C下搅拌 60min， 形成 CuInS2纳米粒子溶液， 并将其冷却至 220°C。
将壳层前驱体溶液快速倒入 CuInS2纳米粒子溶液， 在 220°C下反应
180min后，得到含有 CuInS2/ZnS核壳纳米粒子的溶液，并将其冷却至室温。
加入是含有 CUInS2/ZnS核壳纳米粒子的溶液 3倍体积的丙酮和异丙醇 混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 CuInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶液
(丙酮和异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过程 2 次。 将得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 形成的 CUInS2/ZnS核壳纳米粒子的荧光量子产率为 53.0%，荧光光谱波长为 587nm。 实施例 5: 锌前驱体变化对 CUInS2/ZnS核壳纳米粒子性能影响
混合 0.8662g二乙基二硫代氨基甲酸锌、 3ml 十二硫醇和 6ml 十八 烯溶剂。 将混合物加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.074g醋酸亚铜， 0.175g醋酸铟和 1.50ml 1-十二碳硫醇加入到 15ml二甲苯基醚中， 在氮气气氛下搅拌脱气 30min后， 在 240°C下搅拌 60min， 形成 CuInS2纳米粒子溶液， 并将其冷却至 220°C。
将壳层前驱体溶液快速倒入 CuInS2纳米粒子溶液， 在 220°C下反应 120min后，得到含有 CuInS2/ZnS核壳纳米粒子的溶液，并将其冷却至室温。
加入是含有 CUInS2/ZnS核壳纳米粒子的溶液 4倍体积的丙酮和异丙醇 混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 CUInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶液 (丙酮和异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过程 2 次。 将得到的 CuInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 形成的 CuInS2/ZnS核壳纳米粒子的荧光量子产率为 53.7%，荧光光谱波长为 605nm。 实施例 6: 有机配合物油胺对 CUInS2/ZnS核壳纳米粒子性能影响 混合 0.2205g醋酸锌、 3ml 十二硫醇、 3ml油胺和 6ml 十八烯溶剂。 将混合物加热到 10(TC直至锌盐溶解， 形成壳层前驱体溶液。
将 0.074g醋酸亚铜， 0.175g醋酸铟和 1.50ml 1-十二碳硫醇加入到 15ml二甲苯基醚中， 在氮气气氛下搅拌脱气 30min后， 在 240°C下搅拌 60min, 形成 CuInS^fi米粒子溶液。
将壳层前驱体溶液快速倒入 CuInS2纳米粒子溶液， 在 240°C下反应 60min后， 得到含有 CuInS2/ZnS核壳纳米粒子的溶液， 并将其冷却至室温。
加入是含有 CuInS2/ZnS核壳纳米粒子的溶液 4倍体积的丙酮和异丙醇 混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 CuInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶液 (丙酮和异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过程 2 次。 将得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 形成的 CuInS2/ZnS核壳纳米粒子的荧光量子产率为 20.9%，荧光光谱波长为 576nm。 实施例 7: 有机配合物十八胺对 CUInS2/ZnS核壳纳米粒子性能影响 混合 0.2205g醋酸锌、 3ml 十二硫醇、 3ml十八胺和 6ml 十八烯溶 剂。 将混合物加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.074g醋酸亚铜， 0.175g醋酸铟和 1.50ml 1-十二碳硫醇加入到 15ml 二甲苯基醚中， 在氮气气氛下搅拌脱气 30min后， 在 240°C下搅拌 60min， 形成 CuInS2纳米粒子溶液。
将壳层前驱体溶液快速倒入 CuInS2纳米粒子溶液， 在 240°C下反应 60min后， 得到含有 CuInS2/ZnS核壳纳米粒子的溶液， 并将其冷却至室温。 加入是含有 CuInS2/ZnS核壳纳米粒子的溶液 4倍体积的丙酮和异丙醇 混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 CUInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶液
(丙酮和异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过程 2 次。 将得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 形成的 CUInS2/ZnS核壳纳米粒子的荧光量子产率为 42%， 荧光光谱波长 为 582nm。 实施例 8:有机配合物磷酸三辛酯对 CUInS2/ZnS核壳纳米粒子性能影响 混合 0.2205g醋酸锌、 3ml 十二硫醇、 5ml磷酸三辛酯和 3ml 十八 烯溶剂。 将混合物加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.074g醋酸亚铜， 0.175g醋酸铟和 1.50ml 1-十二碳硫醇加入到 15ml二甲苯基醚中， 在氮气气氛下搅拌脱气 30min后， 在 230Ό下搅拌 60min, 形成 CuInS ^米粒子溶液。
将壳层前驱体溶液快速倒入 CuInS2纳米粒子溶液， 在 230°C下反应 60min后， 得到含有 CuInS2/ZnS核壳纳米粒子的溶液， 并将其冷却至室温。
加入是含有核壳 CuInS2/ZnS纳米粒子的溶液 4倍体积的丙酮和异丙 醇混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心 沉降， 除去离心沉降后的上层溶液， 得到 CuInS2/ZnS核壳纳米粒子沉淀 物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶 液 （丙酮和异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过 程 2次。 将得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下 储存。 形成的 CuInS2/ZnS核壳纳米粒子的荧光量子产率为 38%， 荧光光 谱波长为 594nm。 实施例 9: AgInS2/ZnS核壳纳米粒子的合成
混合 0.220g醋酸锌、 3ml 十二硫醇和 6ml 十八烯溶剂。 将混合物 加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.085g硝酸银， 0.175g醋酸铟和 1.5ml 十二硫醇加入到 15ml 十 八烯溶剂中， 在氮气气氛下搅拌脱气 30min后， 在 240°C下搅拌 15min， 形成 AgInS2纳米粒子溶液。
将壳层前驱体溶液快速倒入 AgInS2纳米粒子溶液， 在 220°C下反应 60min后， 得到含有 AgInS2/ZnS核壳纳米粒子的溶液， 并将其冷却至室温。
加入是含有 AgInS2/ZnS核壳纳米粒子的溶液 4倍体积的丙酮和异丙醇 混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心沉降， 除去离心沉降后的上层溶液， 得到 AgInS2/ZnS核壳纳米粒子沉淀物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶液 (丙酮与异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过程 2 次。 将得到的 AgInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下储存。 实施例 10: ZnCuInS2/ZnS核壳纳米粒子的合成
混合 0.220g醋酸锌、 3ml 十二硫醇和 6ml 十八烯溶剂。 将混合物 加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.076g醋酸亚铜， 0.175g醋酸铟， 0.109g醋酸锌和 1.5ml 十二硫 醇加入到 15ml 十八烯溶剂中，在氮气气氛下搅拌脱气 30min后，在 230°C 下搅拌 90min， 形成 ZnCuInS2纳米粒子溶液。
将壳层前驱体溶液快速倒入 ZnCuInS2纳米粒子溶液， 在 220Ό下反应 60min后， 得到含有 ZnCuInS2/ZnS核壳纳米粒子的溶液， 并将其冷却至室 温。
加入是含有 ZnCuInS2/ZnS核壳纳米粒子的溶液 4倍体积的丙酮和异 丙醇混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离 心沉降， 除去离心沉降后的上层溶液， 得到 ZnCuInS2/ZnS核壳纳米粒子 沉淀物。 将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶 液 （丙酮与异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过 程 2次。 将得到的 CUInS2/ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下 储存。 实施例 11 : CuInS2/ZnS核壳纳米粒子的合成
混合 0.293g醋酸锌、 3ml 十二硫醇和 6ml 十八烯溶剂。 将混合物 加热到 100°C直至锌盐溶解， 形成壳层前驱体溶液。
将 0.051g醋酸亚铜， 0.120g醋酸铟和 1.03ml 十二硫醇加入到 10.3ml 十八烯溶剂中， 在氮气气氛下搅拌脱气 30min后，在 240°C下搅拌 60min， 将其冷却至室温， 加入 33ml的丙酮使 CuInS2纳米粒子溶液离心沉降， 除去 离心沉降后的上层溶液， 得到 CuInS2纳米粒子。
将 0111^2纳米粒子分散在 5ml甲苯中， 加入 20ml的丙酮进行清洗， 再 离心沉降， 重复上述过程 2次。 将得到的 CuInS2纳米粒子分散在 11ml的十 八烯中， 在氮气气氛下搅拌脱气 30min后， 快速升温至 240°C， 快速倒入 壳层前驱体溶液， 加热搅拌 60min后， 得到 CuInS2/ZnS核壳纳米粒子的溶 液， 并将其冷却至室温。
加入是含有 CUInS2/ZnS核壳纳米粒子的溶液 4倍体积的丙酮和异丙 醇混合溶液 （丙酮与异丙醇体积比为 4: 1 ) 形成悬浮液， 将悬浮液离心 沉降， 除去离心沉降后的上层溶液， 得到 CUInS2/ZnS核壳纳米粒子沉淀 物。
将沉淀物分散在甲苯中，加入是甲苯 3倍体积的丙酮和异丙醇混合溶 液 （丙酮与异丙醇体积比为 4: 1 ) 进行清洗， 再离心沉降， 重复上述过 程 2次。 将得到的 CuInS ZnS核壳纳米粒子分散在甲苯中， 在氮气气氛下 储存。 形成的 CuInS2/ZnS核壳纳米粒子的荧光量子产率为 70%， 荧光光 谱波长为 561nm。

Claims

权利要求书
1. 一种制备核壳纳米粒子溶液的方法， 包括以下步骤：
a) 将半导体纳米粒子溶液调节至一预设定的壳层包裹温度； b) 将一壳层前驱体溶液加入到所述半导体纳米粒子溶液中， 并在所 述预设定的壳层包裹温度下进行反应，所述壳层前驱体溶液由包括锌盐、 烷基硫醇和非极性有机溶剂的成分混合形成；
c )在所述反应进行一预设定反应时间后， 得到所述半导体纳米粒子 的核壳纳米粒子溶液；
2. 如权利要求 1所述的制备方法， 其中， 所述烷基硫醇的摩尔含量 大于锌盐摩尔含量。
3. 如权利要求 1或 2所述的制备方法， 其中， 所述垸基硫醇与锌盐 的摩尔比为 (2〜80)： 1。
4. 如权利要求 1所述的制备方法， 其中， 所述垸基硫醇选自带有一 个或者一个以上巯基官能团的硫醇。
5. 如权利要求 4所述的制备方法， 其中， 所述烷基硫醇选自下面的 一种或多种： 辛基硫醇、 异辛基硫醇、 十二烷基硫醇、 十四烷基硫醇、 十六垸基硫醇、 十八垸基硫醇、 1,8-二辛基硫醇和 1,6-二辛基硫醇。
6. 如权利要求 1， 2或 4所述的制备方法， 其中， 所述非极性有机 溶剂选自下面的一种或多种： 十八烯、 十二烷、 十六垸、 十八垸、 二甲 基苯基醚、 氢化三联苯、 石蜡、 二苯醚、 二辛醚和二卞醚。
7. 如权利要求 1、 2或 4所述的制备方法， 其中， 所述壳层包裹温 度为 150°C〜290° (：。
8. 如权利要求 7所述的制备方法， 其中， 所述壳层包裹温度为 200T〜 260°C。
9. 如权利要求 1、 2或 4所述的制备方法， 其中， 所述反应时间为 lmii！〜 4h。
10. 如权利要求 9所述的制备方法， 其中， 所述反应时间为 15min~2h。
1 1. 一种制备核壳纳米粒子的方法， 包括以下步骤：
将权利要求 1- 10中任意一种方法制备的核壳纳米粒子溶液与一极性 溶剂混合形成悬浮液；
分离所述悬浮液得到所述核壳纳米粒子。
12. 如权利要求 1 1所述的制备方法， 进一步包括步骤： 将所述分离 得到的核壳纳米粒子进行至少一次清洗， 以去除杂质。
13. 如权利要求 1 1或 12所述的制备方法， 其中， 所述极性溶剂选自 下面的一种或多种： 甲醇、 乙醇、 异丙醇、 丁醇、 甲乙酮和丙酮。
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