WO2022156467A1 - 一种荧光量子点及其制备方法与应用 - Google Patents

一种荧光量子点及其制备方法与应用 Download PDF

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WO2022156467A1
WO2022156467A1 PCT/CN2021/140056 CN2021140056W WO2022156467A1 WO 2022156467 A1 WO2022156467 A1 WO 2022156467A1 CN 2021140056 W CN2021140056 W CN 2021140056W WO 2022156467 A1 WO2022156467 A1 WO 2022156467A1
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silver
quantum dots
source
gold
selenium
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PCT/CN2021/140056
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English (en)
French (fr)
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王强斌
杨红超
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中国科学院苏州纳米技术与纳米仿生研究所
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Priority claimed from CN202110073230.0A external-priority patent/CN114854416B/zh
Priority claimed from CN202111243959.4A external-priority patent/CN116023928A/zh
Application filed by 中国科学院苏州纳米技术与纳米仿生研究所 filed Critical 中国科学院苏州纳米技术与纳米仿生研究所
Priority to EP21920841.0A priority Critical patent/EP4092095A4/en
Priority to JP2022536547A priority patent/JP7378857B2/ja
Priority to US17/785,420 priority patent/US20230247846A1/en
Publication of WO2022156467A1 publication Critical patent/WO2022156467A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides

Definitions

  • the present application relates to a fluorescent quantum dot and a preparation method thereof, in particular to an alloyed fluorescent quantum dot and a preparation method thereof, as well as a near-infrared silver-gold-selenium fluorescent quantum dot with high quantum efficiency and a preparation method and application thereof, belonging to materials field of science and technology.
  • Fluorescence imaging technology has the advantages of non-contact, intuitive image, real-time, high sensitivity, economical and convenient, and no radiation hazard. According to the wavelength range of fluorescence imaging, it mainly includes visible light fluorescence imaging (400-650 nm) and near-infrared fluorescence imaging (650-1700 nm). In biological imaging, near-infrared light can be divided into two optical windows: near-infrared I region (650-900nm, NIR-I) and near-infrared (900-1700nm, NIR-II). NIR-fluorescence is a new fluorescence window discovered in in vivo fluorescence imaging research in the last decade.
  • NIR-II fluorescence has higher tissue penetration depth and spatial resolution in in vivo imaging.
  • quantum dots As an excellent fluorescent light-emitting material, quantum dots have the following characteristics: high biocompatibility, high quantum efficiency, tunable excitation and emission wavelengths, and easy surface functionalization, etc., and are widely used in in vivo imaging, light-emitting diodes, photodetectors , lasers, photovoltaic cells and other research has a very wide range of applications.
  • the existing fluorescent quantum dots such as lead sulfide, cadmium telluride, lead selenide, mercury telluride, silver selenide, etc., have low absolute fluorescence quantum yields, or some of them contain toxic heavy metal elements. Difficult to have both. Therefore, there is an urgent need to develop a novel fluorescent quantum dot material with continuously tunable single emission, high fluorescence quantum efficiency and high biocompatibility in the visible-near infrared full window (500-1700 nm).
  • the main purpose of the present application is to provide a fluorescent quantum dot with high quantum efficiency and a preparation method and application thereof, so as to overcome the deficiencies in the properties of the existing quantum dots.
  • Embodiments of the present application provide a method for preparing alloyed fluorescent quantum dots, which includes:
  • the second uniform mixing reaction system comprising the silver-based quantum dot precursor, the anion source and/or the metal cation source is subjected to ion exchange reaction at 0-260° C. for 0.4-72 hours to obtain alloyed fluorescent quantum dots.
  • the anion source includes any one or a combination of two or more of a sulfur source, a selenium source, and a tellurium source.
  • the metal elements contained in the metal cation source include any one or a combination of two or more of Mn, Fe, Co, Ni, Cu, Zn, Au, Pd, Pt, and In.
  • the embodiments of the present application also provide alloyed fluorescent quantum dots prepared by the aforementioned method, and the fluorescence emission peak wavelength is located at 500-1700 nm.
  • the absolute quantum efficiency of the alloyed fluorescent quantum dots is greater than 85%.
  • alloyed fluorescent quantum dots include any one or a combination of two or more of AgAuSe, AgAuS, AgAuTe, CuAgS, CuAgSe, and AgInTe 2 .
  • alloyed fluorescent quantum dots include doped alloyed fluorescent quantum dots.
  • alloyed fluorescent quantum dots have a core-shell structure.
  • Embodiments of the present application also provide a method for preparing near-infrared silver-gold-selenium fluorescent quantum dots, which includes:
  • the fourth uniform mixing reaction system comprising the silver selenide quantum dot precursor and the gold source is subjected to a cation exchange reaction at 0-200° C. for 10-72 hours to obtain near-infrared silver-gold-selenium fluorescent quantum dots.
  • the embodiments of the present application also provide near-infrared silver-gold-selenium fluorescent quantum dots prepared by the aforementioned method.
  • the near-infrared silver-gold-selenium fluorescent quantum dots have a diameter of 2-20 nm, a uniform size distribution, and a fluorescence emission peak wavelength of 800-20 nm. 1700nm, the absolute fluorescence quantum yield is greater than 90%.
  • the embodiments of the present application also provide any of the foregoing alloyed fluorescent quantum dots or near-infrared silver-gold-selenium fluorescent quantum dots for use in biological imaging, biomedical or near-infrared devices (such as near-infrared light-emitting diodes, solar cells, photodetectors, lasers) and other fields.
  • biomedical or near-infrared devices such as near-infrared light-emitting diodes, solar cells, photodetectors, lasers
  • silver-based quantum dots including silver selenide quantum dots
  • alloyed quantum dots are obtained by an ion exchange method.
  • the synthesis process steps are simple, the experimental conditions are controllable, and The reagents used are simple and easy to obtain, the yield of the final product is high, and it is suitable for large-scale production;
  • the final product alloyed fluorescent quantum dots prepared in this application have uniform size distribution, and the fluorescence emission is adjustable from visible light to near-infrared, and has excellent photostability, and does not contain any toxic heavy metal elements. Infrared devices and other fields have broad application prospects;
  • the preparation process of the present application can also be extended to the preparation process of other fluorescent quantum dots, and the yield is high, and it is easy to enlarge the reaction scale.
  • Example 1 is a transmission electron microscope photograph of the alloyed fluorescent quantum dots prepared in Example 1 of the present application;
  • Fig. 2 is the visible-near-infrared absorption spectrogram of the alloyed fluorescent quantum dots prepared in Example 1 of the present application;
  • Fig. 4 is the quantum efficiency measurement spectrum of alloyed fluorescent quantum dots prepared in Example 1 of the present application.
  • Fig. 5a-Fig. 5b are the transmission electron microscope photograph and the high-resolution transmission electron microscope photograph of the near-infrared silver-gold-selenium fluorescent quantum dots in Example 13 of the present application respectively;
  • Example 6 is a powder X-ray diffraction pattern of near-infrared silver-gold-selenium fluorescent quantum dots in Example 13 of the present application;
  • Example 7 is an energy dispersive X-ray spectrum of near-infrared silver-gold-selenium fluorescent quantum dots in Example 13 of the present application;
  • 8a-8b are the fluorescence emission spectrum and quantum efficiency measurement spectrum of the near-infrared silver-gold-selenium fluorescent quantum dots in Example 13 of the present application.
  • the second uniform mixing reaction system comprising the silver-based quantum dot precursor, the anion source and/or the metal cation source is subjected to ion exchange reaction at 0-260° C. for 0.4-72 hours to obtain alloyed fluorescent quantum dots.
  • the silver source includes a silver salt including silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver acetate, silver sulfide, silver trifluoroacetate, silver Any one or a combination of two or more of silver ethyl dithiocarbamate, etc., but not limited thereto.
  • the anion source includes any one or a combination of two or more of a sulfur source, a selenium source, and a tellurium source, etc., but is not limited thereto.
  • the sulfur source includes any one or a combination of two or more of sulfur, sodium thiosulfate, sodium sulfide, thiourea, etc., but is not limited thereto.
  • the selenium source includes any one or a combination of two or more of selenium dioxide, selenium, sodium selenate, sodium selenite, sodium selenide, diphenyl diselenide, etc., but not limited to this .
  • the tellurium source includes any one or a combination of two or more of tellurium, sodium telluride, sodium tellurium hydride, etc., but is not limited thereto.
  • the weak polar solvent includes any one of oleylamine, oleic acid, octadecene, octadecylamine, dodecylamine, tetradecylamine, dodecanethiol, octanethiol, octadecanethiol, etc. one or a combination of two or more, but not limited to this.
  • the mass ratio of the silver source to the anion source is 1-10:1-10.
  • the temperature of the solvothermal reaction is 100-300° C., and the time is 0.5-24 h.
  • the silver-based quantum dot precursor may be any one or a combination of two or more of Ag 2 S, Ag 2 Se, Ag 2 Te, etc., but is not limited thereto.
  • the preparation method may include: firstly dissolving silver nitrate in oleylamine, adding a sulfur source, reacting at 200° C. for 1-6 hours, and then cleaning to obtain the target product silver-based Quantum dot precursors.
  • the preparation method may include: dissolving a silver salt with a mass of 0.1-1 g in a weak polar solvent.
  • the preparation method specifically includes: mixing the silver sulfide precursor with a gold source, and reacting at 100° C. to obtain silver-gold-sulfur fluorescent quantum dots.
  • the preparation method further includes: after the reaction is completed, cleaning the obtained silver-gold-sulfur fluorescent quantum dots.
  • the mass ratio of the silver-based quantum dot precursor to the metal cation source is 1-10:1-10.
  • the metal elements contained in the metal cation source may include any one or a combination of two or more of Mn, Fe, Co, Ni, Cu, Zn, Au, Pd, Pt, In, etc., But not limited to this.
  • the metal cation source may include ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, sulfuric acid Nickel, nickel acetate, copper sulfate, copper acetate, copper nitrate, copper chloride, cuprous chloride, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, sodium chloroaurate, chloroauric acid, gold nitrate, chloride Any one or two or more of gold, gold hydroxide, gold oxide, palladium acetate, palladium nitrate, palladium chloride, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, indium acetate, indium chloride, etc. combination, but not limited to this.
  • the aforementioned silver salt, anion source, weak polar solvent, metal cation source, etc. can be selected from, but not limited to, the ones listed above.
  • the preparation method specifically includes:
  • the silver source and the weakly polar solvent are uniformly mixed, and an anion source is added to carry out a solvothermal reaction to obtain a silver-based quantum dot precursor (also called a "silver-based quantum dot precursor");
  • the silver-based quantum dot precursor and the metal cation source are mixed and reacted at 0-260° C. to obtain alloyed fluorescent quantum dots whose fluorescence emission peak wavelength is located at 500-1700 nm.
  • the preparation method of the alloyed fluorescent quantum dots may include the following steps:
  • step II adding sulfur source to the mixed solution finally obtained in step I, mixing and dispersing uniformly, and then reacting at 100-300 ° C for 0.5-24 h;
  • step III isolate the product obtained by step II solvothermal reaction, and clean, dry;
  • step III The product obtained in step III is reacted with a gold source at 0 to 200° C. for 10 to 72 hours to obtain near-infrared silver-gold-sulfur fluorescent quantum dots.
  • the final product alloyed fluorescent quantum dots prepared in this application have uniform size distribution, and their fluorescence emission peak wavelengths are located at 500-1700 nm, preferably 800-1350 nm, and have ultra-high absolute fluorescence quantum efficiency (greater than 85%), and at the same time Does not contain any toxic heavy metal elements. And the yield of the final product is high, and the preparation process is easy to scale up the reaction scale.
  • alloyed fluorescent quantum dots prepared by the aforementioned method which have uniform morphology and size, high absolute quantum yield, and do not contain any toxic heavy metal elements. It has important application prospects in the field of near-infrared devices.
  • alloyed fluorescent quantum dots may preferably include any one or a combination of two or more of AgAuSe, AgAuS, AgAuTe, CuAgS, CuAgSe, AgInTe 2 , etc., but are not limited thereto.
  • alloyed fluorescent quantum dots include doped alloyed fluorescent quantum dots; for example, it may preferably include manganese-doped silver selenide fluorescent quantum dots, nickel-doped silver telluride fluorescent quantum dots, and indium-doped silver sulfide quantum dots Any one or a combination of two or more of fluorescent quantum dots, cobalt-doped silver sulfide fluorescent quantum dots, etc., but not limited thereto.
  • the alloyed fluorescent quantum dots have a core-shell structure; for example, the alloyed fluorescent quantum dots may preferably include Ag 2 S@ZnS, Ag 2 Te@Ag 2 S, Ag 2 Te@Ag 2 Se, Ag 2 Se@Ag 2 S, Ag 2 Se@Ag 2 Te, Ag 2 S@Ag 2 Se, Ag 2 S@Ag 2 Te, Ag 2 Se@ZnS, Ag 2 Se@ZnSe, Ag 2 S@MnS, etc. Any one or a combination of two or more, but not limited to this.
  • Another aspect of the embodiments of the present application also provides a method for preparing near-infrared silver-gold-selenium fluorescent quantum dots, comprising:
  • the fourth uniform mixing reaction system comprising the silver selenide quantum dot precursor and the gold source is subjected to a cation exchange reaction at 0-200° C. for 10-72 hours to obtain near-infrared silver-gold-selenium fluorescent quantum dots.
  • the preparation method mainly includes: uniformly mixing the silver source and the selenium source in a weak polar solvent and performing a solvothermal reaction to prepare the silver selenide quantum dots; It is mixed with gold source and reacted with cation exchange at room temperature to obtain near-infrared silver-gold-selenium quantum dots with high quantum efficiency, and the fluorescence emission peak wavelength is located at 800-1700 nm.
  • the preparation method of the near-infrared silver-gold-selenium fluorescent quantum dots with high quantum efficiency may specifically include:
  • the silver source and the weakly polar solvent are uniformly mixed, and the selenium source is added to carry out a solvothermal reaction to prepare the silver selenide quantum dot precursor;
  • the silver selenide precursor and the gold source are mixed and reacted at 0-200° C. to obtain silver-gold-selenium fluorescent quantum dots, the fluorescence emission peak wavelength is located at 800-1700 nm, and the absolute fluorescence quantum yield is greater than 90%.
  • the preparation method includes: first uniformly mixing the silver source and the weakly polar solvent, and then adding the selenium source to form the third uniform mixing reaction system.
  • the preparation method specifically includes: subjecting the third uniform mixing reaction system to a solvothermal reaction at 100-300° C. for 0.5-24 h to prepare the silver selenide quantum dot precursor.
  • the mass ratio of the silver source to the selenium source is 1-10:1-10. That is, the preparation method includes: dissolving the silver source and the selenium source in a weak polar solvent in a mass ratio of 1-10:1-10.
  • the preparation process of the silver selenide precursor provided in the present application is a solvothermal reaction, the steps are simple, the experimental conditions are controllable, the reagents used are simple and easy to obtain, the yield of the final product is high, and it is suitable for large-scale production.
  • the preparation method includes: uniformly mixing a silver selenide quantum dot precursor, a gold source and a weakly polar solvent to form the fourth uniform mixing reaction system.
  • the mass ratio of the silver selenide quantum dot precursor to the gold source is 1-10:1-10. That is, the preparation method includes: dissolving the silver selenide quantum dot precursor and the gold source in a mass ratio of 1-10:1-10 in a weak polar solvent.
  • the silver salt includes silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver sulfide, silver trifluoroacetate, silver diethyldithiocarbamate, and the like. Any one or a combination of two or more, but not limited to this.
  • the selenium source includes any one or a combination of two or more selected from selenium dioxide, selenium powder, sodium selenate, sodium selenite, sodium selenide, diphenyl diselenide, and the like, But not limited to this.
  • the less polar solvent comprises oleylamine, oleic acid, octadecene, octadecylamine, dodecylamine, tetradecylamine, dodecanethiol, octanethiol, octadecanethiol, and the like Any one or a combination of two or more, but not limited to this.
  • the gold source includes any one or two or more of sodium chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, gold nanorods, gold particles, etc. combination, but not limited to this.
  • the aforementioned silver salts, selenium sources, weak polar solvents, gold sources, and the like may be selected from, but not limited to, those listed above.
  • the preparation method may include: first dissolving silver nitrate in oleylamine, adding a selenium source, reacting at 100-300° C. for 1-6 hours, and then cleaning to obtain the target product silver selenide Quantum dot precursors.
  • the mass ratio of the silver salt to the selenium source is 0.1-1 g:0.1-1 g.
  • the preparation method may include: dissolving silver salt with a mass of 0.1-1 g in a weak polar solvent.
  • the preparation method specifically includes: mixing the silver selenide precursor with a gold source, and reacting at 100-200° C. to obtain near-infrared silver-gold-selenium fluorescent quantum dots.
  • the preparation method further includes: after the reaction is completed, cleaning the obtained silver-gold-selenium fluorescent quantum dots.
  • described preparation method may comprise the following steps:
  • step II After adding the selenium source to the mixed solution finally obtained in step I and mixing and dispersing evenly, the reaction is carried out at 100-300° C. for 0.5-24 h;
  • step III isolate the product obtained by step II solvothermal reaction, and clean, dry;
  • step III The product obtained in step III is reacted with a gold source at 0-200° C. for 10-72 hours to obtain the near-infrared silver-gold-selenium fluorescent quantum dots.
  • silver selenide quantum dots are prepared by a simple high-temperature solvothermal method, and then silver-gold selenium quantum dots are obtained by a cation exchange method.
  • the synthesis process steps are simple, the experimental conditions are controllable, and the reagents used are simple and easy to obtain.
  • the product has a high yield and is suitable for large-scale production.
  • the final product near-infrared silver-gold-selenium fluorescent quantum dots prepared in the present application have uniform size distribution, and their fluorescence emission peak wavelengths are located at 800-1700 nm, preferably 800-1350 nm, and have ultra-high absolute fluorescence quantum efficiency (greater than 90% ), and does not contain any toxic heavy metal elements. And the yield of the final product is high, and the preparation process is easy to scale up the reaction scale.
  • the preparation process of the present application can also be extended to the preparation process of other near-infrared silver-gold-selenium fluorescent quantum dots, and the yield is high, and the reaction scale is easy to be enlarged.
  • the diameter of the near-infrared silver-gold-selenium fluorescent quantum dots is 2-20 nm.
  • the fluorescence emission peak wavelength of the near-infrared silver-gold-selenium fluorescent quantum dots is located at 800-1700 nm, preferably 800-1350 nm, the absolute fluorescence quantum yield is greater than 90%, and does not contain any toxic heavy metal elements.
  • the present application also provides a near-infrared silver-gold-selenium fluorescent quantum dot, which has a uniform shape and size, a high absolute quantum yield, and does not contain any toxic heavy metal elements. It has important application prospects in the fields of biomedicine or near-infrared devices.
  • Another aspect of the embodiments of the present application further provides the use of any of the foregoing alloyed fluorescent quantum dots or near-infrared silver-gold-selenium fluorescent quantum dots in the fields of bioimaging, biomedicine, or near-infrared devices.
  • the near-infrared device may be a near-infrared light emitting diode, a solar cell, a photodetector, a laser, etc., but is not limited thereto.
  • the present application first prepares silver-based quantum dots by a simple high-temperature solvothermal method, and then obtains alloyed quantum dots by an ion exchange method.
  • the synthesis process is simple and controllable, and the yield is high.
  • the fluorescence emission is adjustable from visible light to near-infrared, and has excellent photostability, and does not contain any toxic heavy metal elements, and has wide application prospects in bioimaging, near-infrared devices and other fields.
  • the morphology and size of the near-infrared silver-gold-sulfur fluorescent quantum dot product obtained in this example are uniform, and the size is about 4.5 nm.
  • the above-mentioned silver-gold-sulfur quantum dots were dispersed in chloroform. Using a visible-near-infrared absorption spectrometer to measure its absorption spectrum, it can be seen that quantum dots have strong absorption in the visible to near-infrared region, as shown in Figure 2. The luminescence spectrum and absolute fluorescence quantum yield were further tested using a near-infrared fluorescence spectrometer. It can be seen from FIG. 3 that the emission of the silver-gold-sulfur fluorescent quantum dots is located at 800-1100 nm, and it can be seen from FIG. 4 that its absolute quantum efficiency is 85.15%.
  • Figures 5a-5b the near-infrared silver-gold-selenium fluorescent quantum dots obtained in this example have uniform morphology and size, and the size is about 4.8 nm, wherein Figure 5a is the near-infrared silver-gold-selenium fluorescent quantum dots
  • Figure 5b is a high-resolution transmission electron micrograph.
  • FIG. 6 and FIG. 7 it can be known from powder X-ray diffraction and energy dispersive X-ray spectra that the nanoparticle material is a silver-gold-selenium compound.
  • the above-mentioned silver-gold-selenium quantum dots were dispersed in chloroform. Its luminescence spectrum and absolute fluorescence quantum yield were tested using a near-infrared fluorescence spectrometer. It can be seen from Fig. 8a-Fig. 8b that the emission of the silver-gold-selenium fluorescent quantum dots is located at 800-1200 nm, and the absolute quantum efficiency is 90.3%.
  • 0.06g of silver iodide was added to 20g of octadecylamine, and ultrasonically dispersed evenly, then 0.06g of diphenyl diselenide was added, and the reaction was carried out at 200°C for 24h to obtain a silver selenide quantum dot precursor (0.03g), and then 0.05g of hydroxide was added.
  • Gold react at 0°C for 72h, and near-infrared silver-gold-selenium fluorescent quantum dots can be obtained.
  • the inventors of the present case also used other raw materials and other process conditions listed above to replace the various raw materials and corresponding process conditions in Examples 13-19 to carry out corresponding experiments.
  • the obtained near-infrared silver-gold-selenium fluorescent quantum dots have The morphology and performance are also ideal, and are basically similar to the products of Examples 13-19.
  • silver-based quantum dots are first prepared by a simple high-temperature solvothermal method, and then alloyed quantum dots are obtained by an ion exchange method.
  • the synthesis process is simple and controllable, and the yield is high, and can be prepared on a large scale.
  • the fluorescence emission can be adjusted from visible light to near-infrared, and it has excellent photostability, and does not contain any toxic heavy metal elements, and has wide application prospects in the fields of biological imaging and near-infrared devices.

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Abstract

本申请公开了一种荧光量子点及其制备方法与应用。所述制备方法包括：使包含银源、阴离子源、弱极性溶剂的第一均匀混合反应体系进行溶剂热反应，制得银系量子点前驱体；使包含银系量子点前驱体、阴离子源和/或金属阳离子源的第二均匀混合反应体系进行离子交换反应，获得合金化荧光量子点，其荧光发射峰波长位于500～1700nm，绝对量子效率大于85％。本申请先通过简单的高温溶剂热法制备银系量子点，而后经过离子交换法得到合金化量子点，其合成工艺简单可控，且产率较高，可大规模制备，且荧光发射位于可见光到近红外可调，且具有优越光稳定性，同时不含任何毒性重金属元素，在生物成像、近红外器件等领域有广泛应用前景。

Description

一种荧光量子点及其制备方法与应用
本申请基于并要求于2021年01月20日递交的申请号为202110073230.0、发明名称为“近红外银金硒荧光量子点及其制备方法与应用”，以及于2021年10月25日递交的申请号为202111243959.4、发明名称为“合金化荧光量子点及其制备方法与应用”的两件中国专利申请的优先权。
技术领域
本申请涉及一种荧光量子点及其制备方法，尤其涉及一种合金化荧光量子点及其制备方法以及一种高量子效率的近红外银金硒荧光量子点及其制备方法与应用，属于材料科学技术领域。
背景技术
荧光成像技术具有非接触、图像直观、实时、灵敏度高、经济便捷、无辐射危害等优点，在生物医学研究和临床实践中，特别是在荧光影像手术导航方面具有广泛的应用前景。根据荧光成像的波长范围，其主要包括可见光荧光成像(400-650nm)和近红外荧光成像(650-1700nm)。在生物成像中，近红外光可分为两个光学窗口：近红外I区(650-900nm，NIR-I)和近红外(900-1700nm，NIR-II)。NIR-荧光是最近十年来人们在活体荧光成像研究中发现的一个新的荧光窗口，与可见光区和NIR-I区相比，NIR-II光子在活体组织中的衰减系数显著降低(J.Am.Chem.Soc.2020，142，14789-14804.)，因此，NIR-II荧光在活体成像中具有更高的组织穿透深度和空间分辨率。
量子点作为一种优异的荧光发光材料，具有以下特征：高生物相容性、高量子效率、可调的激发和发射波长和表面易功能化等，而在活体成像，发光二极管，光电探测器，激光器，光伏电池等研究中有着十分广泛的应用。然而，现有的荧光量子点，如硫化铅、碲化镉、硒化铅、碲化汞、硒化银等，其绝对荧光量子产率不高，或者部分含有毒性重金属元素，荧光强度与毒性难以两全。因此，迫切需要开发一种在可见-近红外全窗口(500-1700nm)具有 连续可调单发射的、高荧光量子效率和高生物相容性新型荧光量子点材料。
发明内容
本申请的主要目的在于提供一种高量子效率的荧光量子点及其制备方法与应用，从而克服现有量子点性质中的不足。
为实现前述发明目的，本申请采用的技术方案包括：
本申请实施例提供了一种合金化荧光量子点的制备方法，其包括：
使包含银源、阴离子源、弱极性溶剂的第一均匀混合反应体系进行溶剂热反应，制得银系量子点前驱体；
使包含银系量子点前驱体、阴离子源和/或金属阳离子源的第二均匀混合反应体系于0～260℃进行离子交换反应0.4～72h，获得合金化荧光量子点。
在一些实施例中，所述阴离子源包括硫源、硒源和碲源中的任意一种或两种以上的组合。
在一些实施例中，所述金属阳离子源所含金属元素包括Mn、Fe、Co、Ni、Cu、Zn、Au、Pd、Pt、In中的任意一种或两种以上的组合。
本申请实施例还提供了由前述方法制备的合金化荧光量子点，其荧光发射峰波长位于500～1700nm。
进一步地，所述合金化荧光量子点的绝对量子效率大于85％。
进一步地，所述合金化荧光量子点包括AgAuSe、AgAuS、AgAuTe、CuAgS、CuAgSe、AgInTe 2中的任意一种或两种以上的组合。
进一步地，所述合金化荧光量子点包括掺杂的合金化荧光量子点。
进一步地，所述合金化荧光量子点具有核壳结构。
本申请实施例还提供了一种近红外银金硒荧光量子点的制备方法，其包括：
使包含银源、硒源、弱极性溶剂的第三均匀混合反应体系进行溶剂热反应，制得硒化银量子点前驱体；
使包含硒化银量子点前驱体、金源的第四均匀混合反应体系于0～200℃进行阳离子交换反应10～72h，获得近红外银金硒荧光量子点。
本申请实施例还提供了由前述方法制备的近红外银金硒荧光量子点，所述近红外银金硒荧光量子点的直径为2～20nm，尺寸分布均匀，其荧光发射峰波长位于800～1700nm，绝对荧 光量子产率大于90％。
本申请实施例还提供了前述的任一种合金化荧光量子点或者近红外银金硒荧光量子点于生物成像、生物医学或近红外器件(如近红外发光二极管、太阳能电池、光电探测器、激光器)等领域中的用途。
与现有技术相比，本申请的有益效果在于：
1)本申请先通过简单的高温溶剂热法制备出银系量子点(包括硒化银量子点)，而后经过离子交换法得到合金化量子点，其合成工艺步骤简单，实验条件可控，并且所使用试剂简单易得，终产物产率较高，适于大规模生产；
2)本申请所制备的终产物合金化荧光量子点，尺寸分布均匀，且荧光发射位于可见光到近红外可调，且具有优越光稳定性，同时不含任何毒性重金属元素，在生物成像、近红外器件等领域有广泛应用前景；
3)本申请的制备工艺还可拓展到其它荧光量子点的制备工艺，且产率较高，易于放大反应规模。
附图说明
为了更清楚地说明本申请的技术方案，下面将对实施例或现有技术描述中所需要使用的附图进行简单的介绍，显而易见地，下面描述的附图仅仅作为本文发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他附图。
图1是本申请实施例1中制备的合金化荧光量子点的透射电子显微镜照片；
图2是本申请实施例1中制备的合金化荧光量子点的可见-近红外吸收光谱图；
图3是本申请实施例1中制备的合金化荧光量子点的荧光发射图谱；
图4是本申请实施例1中制备的合金化荧光量子点的量子效率测量图谱；
图5a-图5b分别是本申请实施例13中近红外银金硒荧光量子点的透射电子显微镜照片及高分辨的透射电子显微镜照片；
图6是本申请实施例13中近红外银金硒荧光量子点的粉末X-射线衍射图谱；
图7是本申请实施例13中近红外银金硒荧光量子点的能量色散X射线图谱；
图8a-图8b是本申请实施例13中近红外银金硒荧光量子点的荧光发射图谱和量子效率测 量图谱。
具体实施方式
如前所述，鉴于现有的荧光量子点，如硫化铅、碲化镉、硒化铅、碲化汞、硒化银等，其绝对荧光量子产率不高，同时部分含有毒性重金属元素，荧光强度与毒性难以两全。本案发明人经长期研究和大量实践后发现：一些元素与银基量子点发生离子交换后的合金化量子点，具有很好的光学性质。如下将对本申请的技术方案作更为详细的解释说明。
作为本申请技术方案的一个方面，其所涉及的系一种合金化荧光量子点的制备方法，其包括：
使包含银源、阴离子源、弱极性溶剂的第一均匀混合反应体系进行溶剂热反应，制得银系量子点前驱体；
使包含银系量子点前驱体、阴离子源和/或金属阳离子源的第二均匀混合反应体系于0～260℃进行离子交换反应0.4～72h，获得合金化荧光量子点。
在一些实施方式中，所述银源包括银盐，所述银盐包括氯化银、溴化银、碘化银、硫酸银、硝酸银、碳酸银、乙酸银、硫化银、三氟乙酸银、二乙基二硫代胺基甲酸银等中的任意一种或两种以上的组合，但不限于此。
在一些实施方式中，所述阴离子源包括硫源、硒源和碲源等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述硫源包括硫、硫代硫酸钠、硫化钠、硫脲等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述硒源包括二氧化硒、硒、硒酸钠、亚硒酸钠、硒化钠、二苯基二硒醚等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述碲源包括碲、碲酸钠、碲氢化钠等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述弱极性溶剂包括油胺、油酸、十八烯、十八胺、十二胺、十四胺、十二硫醇、辛硫醇、十八硫醇等中的任意一种或两种以上的组合，但不限于此。
在一些实施方式中，所述银源与阴离子源的质量比为1～10∶1～10。
在一些实施方式中，所述溶剂热反应的温度为100～300℃，时间为0.5～24h。
在一些优选实施方式中，所述银系量子点前驱体可以是Ag 2S、Ag 2Se、Ag 2Te等中的任意一种或两种以上的组合，但不限于此。
进一步地，在一更为典型的实施例之中，所述制备方法可以包括：首先将硝酸银溶于油胺中，加入硫源，200℃反应1～6h，之后清洗，获得目标产物银系量子点前驱体。
在一些较为优选的实施方案之中，所述制备方法可以包括：取质量为0.1～1g的银盐溶于弱极性溶剂中。
进一步地，所述制备方法具体包括：将所述硫化银前驱体与金源混合，100℃反应，获得银金硫荧光量子点。
进一步地，所述制备方法还包括：在反应完成后，对所获银金硫荧光量子点清洗。
在一些实施方式中，所述银系量子点前驱体与金属阳离子源的质量比为1～10∶1～10。
在一些优选实施方式中，所述金属阳离子源所含金属元素可以包括Mn、Fe、Co、Ni、Cu、Zn、Au、Pd、Pt、In等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述金属阳离子源可以包括氯化铁、氯化亚铁、硫酸铁、硫酸亚铁、硝酸铁、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍、乙酸镍、硫酸铜、乙酸铜、硝酸铜、氯化铜、氯化亚铜、乙酸锌、硝酸锌、硫酸锌、氯化锌、氯金酸钠、氯金酸、硝酸金、氯化金、氢氧化金、氧化金、乙酸钯、硝酸钯、氯化钯、氯铂酸、氯铂酸钠、氯铂酸钾、乙酸铟、氯化铟等中的任意一种或两种以上的组合，但不限于此。
其中，前述银盐、阴离子源、弱极性溶剂和金属阳离子源等可选自但不仅限于上文所列的种类。
在一些实施方式中，所述制备方法具体包括：
取银源与弱极性溶剂均匀混合并加入阴离子源，进行溶剂热反应，制得银系量子点前驱体(亦可称为“银基量子点前驱体”)；
将所述银系量子点前驱体与金属阳离子源在0～260℃下混合反应，获得合金化荧光量子点，其荧光发射峰波长位于500～1700nm。
其中，当所述金属阳离子选金源，阴离子源选硫源时，作为一更为具体的实施方案之一，所述合金化荧光量子点的制备方法可以包括以下步骤：
I、取银盐与弱极性溶剂混合后超声均匀分散；
II、向步骤I最终所获混合溶液加入硫源并混合分散均匀后，再于100～300℃反应0.5～24 h；
III、分离出由步骤II溶剂热反应所得产物，并清洗、烘干；
IV、将步骤III所得产物与金源在0～200℃反应10～72h，获得近红外银金硫荧光量子点。
本申请所制备的终产物合金化荧光量子点，尺寸分布均匀，且其荧光发射峰波长位于500～1700nm，优选为800～1350nm，且具有超高的绝对荧光量子效率(大于85％)，同时不含任何毒性重金属元素。并且终产物产率较高，制备工艺易于放大反应规模。
作为本申请技术方案的另一个方面，其还涉及由前述方法制备的合金化荧光量子点，其形貌尺寸均一，绝对量子产率高，且不含任何毒性重金属元素，在生物成像、生物医学或近红外器件领域等方面有着重要的应用前景。
进一步地，所述合金化荧光量子点可以优选包括AgAuSe、AgAuS、AgAuTe、CuAgS、CuAgSe、AgInTe 2等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述合金化荧光量子点包括掺杂的合金化荧光量子点；例如，优选可以包括锰掺杂硒化银荧光量子点、镍掺杂碲化银荧光量子点、铟掺杂硫化银荧光量子点、钴掺杂硫化银荧光量子点等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述合金化荧光量子点具有核壳结构；例如，所述合金化荧光量子点优选可以包括Ag 2S@ZnS、Ag 2Te@Ag 2S、Ag 2Te@Ag 2Se、Ag 2Se@Ag 2S、Ag 2Se@Ag 2Te、Ag 2S@Ag 2Se、Ag 2S@Ag 2Te、Ag 2Se@ZnS、Ag 2Se@ZnSe、Ag 2S@MnS等中的任意一种或两种以上的组合，但不限于此。
本申请实施例的另一个方面还提供了一种近红外银金硒荧光量子点的制备方法，其包括：
使包含银源、硒源、弱极性溶剂的第三均匀混合反应体系进行溶剂热反应，制得硒化银量子点前驱体；
使包含硒化银量子点前驱体、金源的第四均匀混合反应体系于0～200℃进行阳离子交换反应10～72h，获得近红外银金硒荧光量子点。
在一些实施方式中，所述制备方法主要包括：取银源与硒源于弱极性溶剂中均匀混合并进行溶剂热反应，制得硒化银量子点；将如上所述硒化银量子点与金源混合，室温阳离子交换反应，获得高量子效率的近红外银金硒量子点，其荧光发射峰波长位于800～1700nm。
在一些优选实施方式中，所述高量子效率的近红外银金硒荧光量子点的制备方法可具体包括：
取银源与弱极性溶剂均匀混合并加入硒源进行溶剂热反应，制得硒化银量子点前驱体；
将所述硒化银前驱体与金源在0～200℃下混合反应，获得银金硒荧光量子点，其荧光发射峰波长位于800～1700nm，绝对荧光量子产率大于90％。
在一些实施方式中，所述制备方法包括：先将银源与弱极性溶剂均匀混合，之后加入硒源，形成所述第三均匀混合反应体系。
在一些实施方式中，所述制备方法具体包括：使所述第三均匀混合反应体系于100～300℃进行溶剂热反应0.5～24h，制得所述硒化银量子点前驱体。
在一些实施方式中，所述银源与硒源的质量比为1～10∶1～10。亦即，所述制备方法包括：取质量比为1～10∶1～10银源与硒源溶于弱极性溶剂。
本申请提供的硒化银前驱体制备过程为溶剂热反应，步骤简单，实验条件可控，并且所使用试剂简单易得，终产物产率较高，适于大规模生产。
在一些实施方式中，所述制备方法包括：将硒化银量子点前驱体、金源与弱极性溶剂均匀混合，形成所述第四均匀混合反应体系。
在一些实施方式中，所述硒化银量子点前驱体与金源的质量比为1～10∶1～10。亦即，所述制备方法包括：取质量比为1～10∶1～10的硒化银量子点前驱体与金源溶于弱极性溶剂。
在一些实施方式中，所述银盐包括氯化银、溴化银、碘化银、硫酸银、硝酸银、碳酸银、硫化银、三氟乙酸银、二乙基二硫代胺基甲酸银等中的任意一种或两种以上的组合，但不限于此。
在一些实施方式中，所述硒源包括二氧化硒、硒粉、硒酸钠、亚硒酸钠、硒化钠、二苯基二硒醚等中的任意一种或两种以上的组合，但不限于此。
在一些实施方式中，所述弱极性溶剂包括油胺、油酸、十八烯、十八胺、十二胺、十四胺、十二硫醇、辛硫醇、十八硫醇等中的任意一种或两种以上的组合，但不限于此。
在一些实施方式中，所述金源包括氯金酸钠、氯金酸、硝酸金、氯化金、氢氧化金、氧化金、金纳米棒、金颗粒等中的任意一种或两种以上的组合，但不限于此。
前述银盐、硒源、弱极性溶剂和金源等可选自但不仅限于上文所列的种类。
进一步地，在一典型实施例之中，所述制备方法可以包括：首先将硝酸银溶于油胺中，加入硒源，100～300℃反应1～6h，之后清洗，获得目标产物硒化银量子点前驱体。
进一步地，所述银盐与硒源的质量比为0.1～1g∶0.1～1g。
在一些较为优选的实施方案之中，所述制备方法可以包括：取质量为0.1～1g的银盐溶于弱极性溶剂中。
进一步地，所述制备方法具体包括：将所述硒化银前驱体与金源混合，100～200℃反应，获得近红外银金硒荧光量子点。
进一步地，所述制备方法还包括：在反应完成后，对所获银金硒荧光量子点清洗。
其中，作为一更为具体的实施方案之一，所述制备方法可以包括以下步骤：
I、取银盐与弱极性溶剂混合后超声均匀分散；
II、向步骤I最终所获混合溶液加入硒源并混合分散均匀后，再于100～300℃反应0.5～24h；
III、分离出由步骤II溶剂热反应所得产物，并清洗、烘干；
IV、将步骤III所得产物与金源在0～200℃反应10～72h，获得所述近红外银金硒荧光量子点。
本申请先通过简单的高温溶剂热法制备出硒化银量子点，而后经过阳离子交换法得到银金硒量子点，其合成工艺步骤简单，实验条件可控，并且所使用试剂简单易得，终产物产率较高，适于大规模生产。
本申请所制备的终产物近红外银金硒荧光量子点，尺寸分布均匀，且其荧光发射峰波长位于800～1700nm，优选为800～1350nm，且具有超高的绝对荧光量子效率(大于90％)，同时不含任何毒性重金属元素。并且终产物产率较高，制备工艺易于放大反应规模。
进一步地，本申请的制备工艺还可拓展到其它近红外银金硒荧光量子点的制备工艺，且产率较高，易于放大反应规模。
作为本申请技术方案的另一个方面，其还涉及由前述方法制备的近红外银金硒荧光量子点。
进一步地，所述近红外银金硒荧光量子点的直径为2～20nm。
进一步地，所述近红外银金硒荧光量子点的荧光发射峰波长位于800～1700nm，优选为800～1350nm，绝对荧光量子产率大于90％，同时不含任何毒性重金属元素。
作为本申请技术方案的另一个方面，本申请还提供了一种近红外银金硒荧光量子点，其形貌尺寸均一，绝对量子产率高，且不含任何毒性重金属元素，在生物成像、生物医学或近红外器件领域等方面有着重要的应用前景。
本申请实施例的另一个方面还提供了前述的任一种合金化荧光量子点或者近红外银金硒荧光量子点于生物成像、生物医学或近红外器件等领域中的用途。
进一步地，所述近红外器件可以是近红外发光二极管、太阳能电池、光电探测器、激光器等，但不限于此。
综上所述，藉由前述技术方案，本申请先通过简单的高温溶剂热法制备银系量子点，而后经过离子交换法得到合金化量子点，其合成工艺简单可控，且产率较高，可大规模制备，且荧光发射位于可见光到近红外可调，且具有优越光稳定性，同时不含任何毒性重金属元素，在生物成像、近红外器件等领域有广泛应用前景。
为使本申请的目的、技术方案和优点更加清楚，下面结合若干优选实施例对本申请的技术方案进行进一步具体描述，但本申请并不仅仅局限于下述实施例，该领域技术人员在本申请核心指导思想下做出的非本质改进和调整，仍然属于本申请的保护范围。若非特别说明，则下列实施例中使用的各种试剂均是本领域技术人员熟知的，并可以通过市场购买等途径获取。而下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。
实施例1
将0.06g的硝酸银溶于20mL油胺中，超声分散均匀，随后加入0.06硫粉，200℃反应5h，得到硫化银前驱体，接着加入0.06g氯金酸，100℃反应48h，即可得到银金硫荧光量子点。
从图1中可以看出，本实施例所获的近红外银金硫荧光量子点产物的形貌尺寸均一，且尺寸约为4.5nm。
取上述银金硫量子点分散于氯仿中。使用可见-近红外吸收光谱仪测量其吸收光谱，可知量子点在可见到近红外区具有较强的吸收，如图2所示。进一步使用近红外荧光光谱仪测试其发光光谱和绝对荧光量子产率。从图3可知，该银金硫荧光量子点发射位于800～1100nm，图4中可以看出其绝对量子效率为85.15％。
实施例2
将0.06g的乙酸银溶于20mL油酸中，超声分散均匀，随后加入0.6硫粉，250℃反应0.5h，得到硫化银前驱体，接着加入0.6g氯化亚铜，200℃反应10h，即可得到银铜硫荧光量子点。
实施例3
将0.6g的硝酸银溶于20mL十八硫醇中，超声分散均匀，随后加入0.6g碲粉，150℃反应5h，得到碲化银前驱体，接着加入0.6g硒粉，100℃反应24h，即可得到银硒碲荧光量子点。
实施例4
将0.06g的三氟乙酸银溶于20mL十二胺中，超声分散均匀，随后加入0.06硒粉，180℃反应10h，得到硒化银前驱体，接着加入0.06g氯铂酸，0℃反应72h，即可得到银铂硒荧光量子点。
实施例5
将0.06g的氯化银溶于20mL辛硫醇中，超声分散均匀，随后加入0.6硫粉，200℃反应12h，得到硫化银前驱体，接着加入0.06g氯化亚铁，0℃反应72h，即可得到银铁硒荧光量子点。
实施例6
将0.6g的硫化银溶于20mL十六胺中，超声分散均匀，随后加入0.06硒粉，200℃反应5h，得到硒化银前驱体，接着加入0.06g氯化钯，0℃反应72h，即可得到钯银硒荧光量子点。
实施例7
将0.06g的碘化银溶于20mL油胺中，超声分散均匀，随后加入0.06硒粉，200℃反应5h，得到硒化银前驱体，接着加入0.06g氯化锰，0℃反应72h，即可得到锰掺杂硒化银荧光量子点。
实施例8
将0.06g的乙酸银溶于20mL油胺中，超声分散均匀，随后加入0.06硒粉，300℃反应0.5h，得到硒化银前驱体，接着加入0.06g硫粉，100℃反应72h，即可得到Ag 2Se@Ag 2S荧光量子点。
实施例9
将0.6g的硫酸银溶于20mL十八硫醇中，超声分散均匀，随后加入0.06g碲粉，150℃反应1h，得到碲化银前驱体，接着加入0.6g硫粉和0.06g乙酸锌，260℃反应0.4h，即可得到Ag 2Te@ZnS荧光量子点。
实施例10
将0.5g的二乙基二硫代氨基甲酸银溶于20mL十八硫醇中，超声分散均匀，随后加入0.06g碲粉，200℃反应1h，得到碲化银前驱体，接着加入0.06g乙酸镍，150℃反应2h，即可得到镍掺杂碲化银荧光量子点。
实施例11
将0.04g的乙酸银溶于20mL十二硫醇中，超声分散均匀，随后加入0.06g硫粉，200℃反应1h，得到硫化银前驱体，接着加入0.06g乙酸铟，150℃反应2h，即可得到铟掺杂硫化银荧光量子点。
实施例12
将0.06g的碳酸银溶于20mL十二硫醇中，超声分散均匀，随后加入0.06硫粉，100℃反应24h，得到硫化银前驱体，接着加入0.06g氯化钴，100℃反应48h，即可得到钴掺杂硫化银荧光量子点。
此外，本案发明人还利用前文所列出的其它原料以及其它工艺条件等替代实施例1-12中的各种原料及相应工艺条件进行了相应试验，所获合金化荧光量子点的形貌、性能等亦较为理想，基本与实施例1-12产品相似。
实施例13
将0.06g的硝酸银溶于20mL油胺中，超声分散均匀，随后加入0.06硒粉，200℃反应5h，得到硒化银量子点前驱体(0.6g)，接着加入0.06g氯金酸，100℃反应48h，即可得到近红外银金硒荧光量子点。
从图5a-图5b中可以看出，本实施例所获的近红外银金硒荧光量子点产物形貌尺寸均一，且尺寸约为4.8nm，其中图5a是近红外银金硒荧光量子点的透射电子显微镜照片，图5b是高分辨的透射电子显微镜照片。再请参阅图6和图7，通过粉末X射线衍射和能量色散X射线图谱可知，该纳米粒子材料为银金硒化合物。
取上述银金硒量子点分散于氯仿中。使用近红外荧光光谱仪测试其发光光谱和绝对荧光量子产率。从图8a-图8b可知，该银金硒荧光量子点发射位于800～1200nm，绝对量子效率为90.3％。
实施例14
将0.06g碳酸银溶于20mL辛硫醇中，超声分散均匀，随后加入0.8g二氧化硒，250℃ 反应2h，得到硒化银量子点前驱体(0.05g)，接着加入0.5g硝酸金200℃反应10h，即可得到近红外银金硒荧光量子点。
实施例15
将0.6g的溴化银溶于20mL油酸中，超声分散均匀，随后加入0.6硒酸钠，200℃反应1h，得到硒化银量子点前驱体(0.1g)，接着加入0.1g氯金酸钠，100℃反应48h，即可得到近红外银金硒荧光量子点。
实施例16
将0.06g的氯化银溶于20mL十二硫醇中，超声分散均匀，随后加入0.06硒化钠，100℃反应5h，得到硒化银量子点前驱体(0.06g)，接着加入0.06g氯化金，0℃反应72h，即可得到近红外银金硒荧光量子点。
实施例17
将0.06g的碘化银加入20g十八胺中，超声分散均匀，随后加入0.06二苯基二硒醚，200℃反应24h，得到硒化银量子点前驱体(0.03g)，接着加入0.05g氢氧化金，0℃反应72h，即可得到近红外银金硒荧光量子点。
实施例18
将0.06g的二乙基二硫代胺基甲酸银溶于20mL十八硫醇中，超声分散均匀，随后加入0.06硒粉，300℃反应0.5h，得到硒化银量子点前驱体(0.06g)，接着加入0.06g氧化金，0℃反应72h，即可得到近红外银金硒荧光量子点。
实施例19
将0.06g的三氟乙酸银溶于20mL十八烯中，超声分散均匀，随后加入0.06硒粉，200℃反应24h，得到硒化银量子点前驱体(0.06g)，接着加入0.06g金纳米棒，0℃反应72h，即可得到近红外银金硒荧光量子点。
此外，本案发明人还利用前文所列出的其它原料以及其它工艺条件等替代实施例13-19中的各种原料及相应工艺条件进行了相应试验，所获近红外银金硒荧光量子点的形貌、性能等亦较为理想，基本与实施例13-19产品相似。
综上所述，本申请先通过简单的高温溶剂热法制备银系量子点，而后经过离子交换法得到合金化量子点，其合成工艺简单可控，且产率较高，可大规模制备，且荧光发射位于可见光到近红外可调，且具有优越光稳定性，同时不含任何毒性重金属元素，在生物成像、近红 外器件等领域有广泛应用前景。
以上所述的实施例对本申请的技术方案进行了详细说明，应理解的是以上所述仅为本申请的具体实施例，并不用于限制本申请，凡在本申请的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本申请的保护范围之内。
尽管已参考说明性实施例描述了本申请，但所属领域的技术人员将理解，在不背离本申请的精神及范围的情况下可做出各种其它改变、省略及/或添加且可用实质等效物替代所述实施例的元件。另外，可在不背离本申请的范围的情况下做出许多修改以使特定情形或材料适应本申请的教示。因此，本文并不打算将本申请限制于用于执行本申请的所揭示特定实施例，而是打算使本申请将包含归属于所附权利要求书的范围内的所有实施例。此外，除非具体陈述，否则术语第一、第二等的任何使用不表示任何次序或重要性，而是使用术语第一、第二等来区分一个元素与另一元素。

Claims (15)

  1. 一种合金化荧光量子点的制备方法，其特征在于包括：
    使包含银源、阴离子源、弱极性溶剂的第一均匀混合反应体系进行溶剂热反应，制得银系量子点前驱体；
    使包含银系量子点前驱体、阴离子源和/或金属阳离子源的第二均匀混合反应体系于0～260℃进行离子交换反应0.4～72h，获得合金化荧光量子点。
  2. 根据权利要求1所述的制备方法，其特征在于：所述银源包括银盐，所述银盐包括氯化银、溴化银、碘化银、硫酸银、硝酸银、碳酸银、乙酸银、硫化银、三氟乙酸银、二乙基二硫代胺基甲酸银中的任意一种或两种以上的组合。
  3. 根据权利要求1所述的制备方法，其特征在于：所述阴离子源包括硫源、硒源和碲源中的任意一种或两种以上的组合；优选的，所述硫源包括硫、硫代硫酸钠、硫化钠、硫脲中的任意一种或两种以上的组合，优选的，所述硒源包括二氧化硒、硒、硒酸钠、亚硒酸钠、硒化钠、二苯基二硒醚中的任意一种或两种以上的组合，优选的，所述碲源包括碲、碲酸钠、碲氢化钠中的任意一种或两种以上的组合。
  4. 根据权利要求1所述的制备方法，其特征在于：所述弱极性溶剂包括油胺、油酸、十八烯、十八胺、十二胺、十四胺、十二硫醇、辛硫醇、十八硫醇中的任意一种或两种以上的组合。
  5. 根据权利要求1所述的制备方法，其特征在于：所述银源与阴离子源的质量比为1～10∶1～10。
  6. 根据权利要求1所述的制备方法，其特征在于：所述溶剂热反应的温度为100～300℃，时间为0.5～24h。
  7. 根据权利要求1所述的制备方法，其特征在于：所述银系量子点前驱体包括Ag 2S、Ag 2Se、Ag 2Te中的任意一种或两种以上的组合；和/或，所述银系量子点前驱体与金属阳离子源的质量比为1～10∶1～10。
  8. 根据权利要求1所述的制备方法，其特征在于：所述金属阳离子源所含金属元素包括Mn、Fe、Co、Ni、Cu、Zn、Au、Pd、Pt、In中的任意一种或两种以上的组合，优选的，所述金属阳离子源包括氯化铁、氯化亚铁、硫酸铁、硫酸亚铁、硝酸铁、氯化钴、硝酸钴、硫 酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍、乙酸镍、硫酸铜、乙酸铜、硝酸铜、氯化铜、氯化亚铜、乙酸锌、硝酸锌、硫酸锌、氯化锌、氯金酸钠、氯金酸、硝酸金、氯化金、氢氧化金、氧化金、乙酸钯、硝酸钯、氯化钯、氯铂酸、氯铂酸钠、氯铂酸钾、乙酸铟、氯化铟中的任意一种或两种以上的组合。
  9. 由权利要求1-8中任一项所述方法制备的合金化荧光量子点，其荧光发射峰波长位于500～1700nm，优选为800～1350nm，所述合金化荧光量子点的绝对量子效率大于85％，优选的，所述合金化荧光量子点包括AgAuSe、AgAuS、AgAuTe、CuAgS、CuAgSe、AgInTe 2中的任意一种或两种以上的组合；
    优选的，所述合金化荧光量子点包括掺杂的合金化荧光量子点；优选包括锰掺杂硒化银荧光量子点、镍掺杂碲化银荧光量子点、铟掺杂硫化银荧光量子点、钴掺杂硫化银荧光量子点中的任意一种或两种以上的组合；
    优选的，所述合金化荧光量子点具有核壳结构；尤其优选的，所述合金化荧光量子点包括Ag 2S@ZnS、Ag 2Te@Ag 2S、Ag 2Te@Ag 2Se、Ag 2Se@Ag 2S、Ag 2Se@Ag 2Te、Ag 2S@Ag 2Se、Ag 2S@Ag 2Te、Ag 2Se@ZnS、Ag 2Se@ZnSe、Ag 2S@MnS中的任意一种或两种以上的组合。
  10. 一种近红外银金硒荧光量子点的制备方法，其特征在于包括：
    使包含银源、硒源、弱极性溶剂的第三均匀混合反应体系进行溶剂热反应，制得硒化银量子点前驱体；
    使包含硒化银量子点前驱体、金源的第四均匀混合反应体系于0～200℃进行阳离子交换反应10～72h，获得近红外银金硒荧光量子点。
  11. 根据权利要求10所述的制备方法，其特征在于包括：先将银源与弱极性溶剂均匀混合，之后加入硒源，形成所述第三均匀混合反应体系，使所述第三均匀混合反应体系于100～300℃进行溶剂热反应0.5～24h优选1～6h，制得所述硒化银量子点前驱体；
    和/或，所述银源与硒源的质量比为1～10∶1～10。
  12. 根据权利要求10所述的制备方法，其特征在于包括：将硒化银量子点前驱体、金源与弱极性溶剂均匀混合，形成所述第四均匀混合反应体系；
    和/或，所述硒化银量子点前驱体与金源的质量比为1～10∶1～10。
  13. 根据权利要求10所述的制备方法，其特征在于：所述银盐包括氯化银、溴化银、碘化银、硫酸银、硝酸银、碳酸银、硫化银、三氟乙酸银、二乙基二硫代胺基甲酸银中的任意 一种或两种以上的组合；
    和/或，所述硒源包括二氧化硒、硒粉、硒酸钠、亚硒酸钠、硒化钠、二苯基二硒醚中的任意一种或两种以上的组合；
    和/或，所述弱极性溶剂包括油胺、油酸、十八烯、十八胺、十二胺、十四胺、十二硫醇、辛硫醇、十八硫醇中的任意一种或两种以上的组合；
    和/或，所述金源包括氯金酸钠、氯金酸、硝酸金、氯化金、氢氧化金、氧化金、金纳米棒、金颗粒中的任意一种或两种以上的组合。
  14. 由权利要求10-13中任一项所述方法制备的近红外银金硒荧光量子点，所述近红外银金硒荧光量子点的直径为2～20nm，尺寸分布均匀，其荧光发射峰波长位于800～1700nm，优选为800～1350nm，绝对荧光量子产率大于90％。
  15. 权利要求9所述的合金化荧光量子点或权利要求14所述的近红外银金硒荧光量子点于生物成像、生物医学或近红外器件领域中的应用，优选的，所述近红外器件包括近红外发光二极管、太阳能电池、光电探测器或激光器。
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