WO2020211834A1 - 利用新型磷前驱体制备磷化铟纳米晶的方法及其制备的磷化铟纳米晶 - Google Patents

利用新型磷前驱体制备磷化铟纳米晶的方法及其制备的磷化铟纳米晶 Download PDF

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WO2020211834A1
WO2020211834A1 PCT/CN2020/085274 CN2020085274W WO2020211834A1 WO 2020211834 A1 WO2020211834 A1 WO 2020211834A1 CN 2020085274 W CN2020085274 W CN 2020085274W WO 2020211834 A1 WO2020211834 A1 WO 2020211834A1
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indium phosphide
precursor
indium
solution
nanocrystal
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PCT/CN2020/085274
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English (en)
French (fr)
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单玉亮
曹越峰
杨涵妮
邝青霞
王允军
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苏州星烁纳米科技有限公司
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Priority claimed from CN201910311285.3A external-priority patent/CN111826158B/zh
Priority claimed from CN201910388638.XA external-priority patent/CN111909699B/zh
Priority claimed from CN201910574567.2A external-priority patent/CN112143497B/zh
Priority claimed from CN201910574541.8A external-priority patent/CN112143496B/zh
Application filed by 苏州星烁纳米科技有限公司 filed Critical 苏州星烁纳米科技有限公司
Priority to KR1020217037707A priority Critical patent/KR20220002392A/ko
Priority to JP2021561728A priority patent/JP7470135B2/ja
Priority to US17/604,452 priority patent/US11827827B2/en
Publication of WO2020211834A1 publication Critical patent/WO2020211834A1/zh

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Definitions

  • This application belongs to the field of nanomaterials, and in particular relates to a method for preparing indium phosphide nanocrystals by using a novel phosphorus precursor as a raw material and different wavelengths of indium phosphide nanocrystals prepared by this method.
  • nanocrystals Compared with organic fluorescent dyes, nanocrystals have the advantages of photobleaching resistance, high quantum yield, and narrow half-peak width, and have huge application prospects in the fields of display, lighting and biological imaging.
  • quantum dots of group II-VI elements cadmium selenide, cadmium telluride, etc.
  • quantum dots of group II-VI elements contain highly toxic elements such as cadmium, which have obvious neurotoxicity and limit the application of such quantum dots.
  • III-V group element quantum dots represented by indium phosphide quantum dots do not have inherent toxicity and have a wider range of applications, and are gradually receiving attention from scientific research and industry circles.
  • the emission wavelength of indium phosphide quantum dots synthesized in the prior art is generally 500-700 nm, which limits its application in the wavelength range above 700 nm and below 500 nm.
  • the optical properties of the indium phosphide nanocrystals synthesized in the prior art such as luminous efficiency, half-width of the fluorescence emission peak, etc., still have a very obvious gap with respect to the II-VI group element nanocrystals.
  • this application provides a method for preparing indium phosphide nanocrystals.
  • a method for preparing indium phosphide nanocrystals which includes the steps of using M-(OC ⁇ P)n as one of the reaction precursors, where M is a metal element, and n is an element of M
  • M is a metal element
  • n is an element of M
  • M-(OC ⁇ P)n is Li-OC ⁇ P, Na-OC ⁇ P, KOC ⁇ P, Zn-(OC ⁇ P) 2 or Ga-(OC ⁇ P) 3 .
  • indium phosphide nanocrystals contain M, In, and P elements, and optionally Zn.
  • the reaction precursor also includes an indium precursor.
  • the reaction precursor also includes a zinc precursor.
  • the method includes the steps of: subjecting a solution containing an indium precursor, M-(OC ⁇ P)n, an optional zinc precursor, and a solvent to high temperature treatment to obtain indium phosphide nanocrystalline nuclei, and the high temperature reaction temperature is Between 150°C and 340°C, preferably between 150°C and 300°C.
  • the method includes the step of coating a shell layer on the nanocrystalline core.
  • the solvent is a coordination compound.
  • the coordination compound is an amine or a carboxylic acid.
  • an indium phosphide nanocrystal prepared by the above-mentioned preparation method.
  • This application uses M-(OC ⁇ P) n as one of the reaction precursors. Since the metal element M and the P element come from the same reaction precursor, it is possible to prepare the nanocrystalline nuclei containing In, P and the metal element M. Crystal, the prepared indium phosphide nanocrystal has a wide light-emitting wavelength range and excellent light-emitting performance.
  • the application also provides a method for preparing near-infrared indium phosphide nanocrystals.
  • a method for preparing near-infrared indium phosphide nanocrystals including the steps of: S1, obtaining a first solution system containing an indium precursor and a second solution system containing a phosphorus precursor; S2 At a predetermined temperature, the first solution system containing the indium precursor and the second solution system containing the phosphorus precursor are mixed and reacted to obtain indium phosphide nanocrystals; wherein the first solution system containing the indium precursor includes the indium precursor And the first organic solvent for dispersing the indium precursor, the second solution system containing the phosphorus precursor includes the phosphorus precursor and the second organic solvent for dispersing the phosphorus precursor, the first organic solvent is different from the second organic solvent, and the second organic solvent The boiling point of the solvent is below the predetermined temperature.
  • the boiling point of the second organic solvent is at least 30°C lower than the predetermined temperature; preferably, the synthesis method further includes step S3, adding the precursor material required for synthesizing the shell of the nanocrystal into the reaction system of S2, in the near infrared
  • the surface of the indium phosphide nanocrystal forms a shell, so that the fluorescence emission peak of the near-infrared indium phosphide nanocrystal is 700-900nm.
  • the predetermined temperature ranges from 180 to 320°C, and the boiling point of the second organic solvent is 60 to 150°C.
  • the chemical structural formula of the phosphorus precursor is M—(O—C ⁇ P) n , where M is a metal element, and n is 1, 2 or 3.
  • the second organic solvent includes at least one of benzene, toluene, cyclohexane, n-hexane, n-heptane, n-octane, tetrahydrofuran, and chloroform.
  • the indium precursor is indium halide.
  • the first organic solvent is at least one of saturated or unsaturated amines with carbon number ⁇ 6.
  • the first solution system containing the indium precursor also includes a zinc precursor. Further, a shell layer is coated on the indium phosphide nanocrystal.
  • a near-infrared indium phosphide nanocrystal prepared by the above-mentioned preparation method. Furthermore, the emission peak of the near-infrared indium phosphide nanocrystal is 700-900 nm.
  • a novel phosphorus precursor is used, and the first solution system containing the indium precursor and the second solution system containing the phosphorus precursor are mixed and reacted at a predetermined temperature, and the second organic solvent is The boiling point is lower than the predetermined temperature, so that indium phosphide nanocrystals with a wavelength range of 700 to 900 nm can be directly obtained in one step, which realizes the application of indium phosphide nanocrystals in the near-infrared wavelength range, thereby broadening the application range of indium phosphide nanocrystals .
  • This application provides a method for preparing red light indium phosphide nanocrystals with good optical performance.
  • a method for preparing red light indium phosphide nanocrystals which includes the steps of: S1, mixing an indium precursor, a phosphorus precursor, and an organic solvent, reacting at a first temperature, and holding for a period of time , Obtain the indium phosphide nanocrystalline core solution; S2, rapidly heat the indium phosphide nanocrystalline core solution to the second temperature, and keep it for a period of time; S3, add the precursor required for the synthesis of the nanocrystalline shell into the reaction system of S2 The red light indium phosphide nanocrystal is obtained, and the fluorescence emission peak of the red light indium phosphide nanocrystal is 580-670 nm.
  • the range of the first temperature is 110-160°C.
  • the range of the second temperature is 280-340°C.
  • the indium phosphide nanocrystal nucleus solution is rapidly heated to the second temperature and maintained for at least 10 minutes.
  • the organic solvent is selected from at least one of saturated or unsaturated amines with carbon number ⁇ 6.
  • the chemical structural formula of the phosphorus precursor is M—(O—C ⁇ P) n , where M is a metal element, and n is 1, 2 or 3.
  • the indium phosphide nanocrystalline nucleus solution contains the first zinc precursor.
  • the first zinc precursor is selected from zinc halides.
  • the ratio of the first zinc precursor to the indium precursor is (0.01-10):1 based on the amount of the substance.
  • the shell of the nanocrystal includes at least one of ZnS, ZnSe, and ZnSeS.
  • a red light indium phosphide nanocrystal is provided, which is prepared by the above preparation method.
  • the fluorescence emission peak value of the red light indium phosphide nanocrystal is 580-670 nm.
  • This application adopts the preparation method of "low-temperature nucleation-rapid heating-assisted nucleus growth-final cladding" to obtain red indium phosphide nanocrystals with a fluorescence emission peak at 580-670 nm, and its fluorescence emission peak half-width is small ( ⁇ 50nm), high fluorescence quantum yield (>80%), and meet the application requirements of indium phosphide nanocrystals.
  • This application provides a method for preparing cyan indium phosphide nanocrystals with high fluorescence quantum yield.
  • a method for preparing cyan indium phosphide nanocrystals including the steps of: S1, mixing an indium precursor, a phosphorus precursor, and an organic solvent, and reacting at a first temperature to obtain indium phosphide Nanocrystalline nucleus solution; S2, at the first temperature, add zinc cation precursor to the indium phosphide nanocrystalline nucleus solution to form a first mixed solution; S3, at the second temperature, add sulfur or Selenium anion precursor, the cation precursor reacts with the anion precursor to form the indium phosphide nanocrystal core coating shell layer, and the blue light indium phosphide nanocrystal is obtained.
  • the fluorescence emission peak of the blue light indium phosphide nanocrystal is 460 ⁇ 500nm ; Wherein, the second temperature is greater than the first temperature.
  • the range of the first temperature is 110-160°C.
  • the second temperature ranges from 160 to 240°C, preferably 160 to 200°C.
  • the organic solvent is selected from at least one of saturated or unsaturated amines with carbon number ⁇ 6.
  • the chemical structural formula of the phosphorus precursor is M—(O—C ⁇ P) n , where M is a metal element, and n is 1, 2 or 3.
  • the indium phosphide nanocrystalline nucleus solution contains the first zinc precursor.
  • the first zinc precursor is selected from zinc halides.
  • the ratio of the cation precursor in step S2 to the indium precursor in step S1 is (8-40):1 in terms of the amount of substance.
  • the cationic precursor is a second zinc precursor; the second zinc precursor is selected from zinc carboxylate or organic zinc.
  • the anion precursor is at least one of a sulfur precursor and a selenium precursor.
  • a cyan indium phosphide nanocrystal is provided, which is prepared by the above preparation method.
  • the fluorescence emission peak value of the cyan indium phosphide nanocrystal is 460-500 nm.
  • cyan indium phosphide nanocrystals with a wavelength range of 460-500 nm can be obtained.
  • the fluorescence quantum yield of the indium phosphide nanocrystal is high (>50%), thereby broadening the application range of the indium phosphide nanocrystal.
  • the preparation method of the present application has simple operation and high efficiency, meets the needs of large-scale production, and has high value for realizing the practical application of high-quality indium phosphide nanocrystalline materials in the next generation of displays.
  • FIG. 1 is a schematic diagram of the structure of nanocrystals in an exemplary embodiment of the application
  • Figure 2 is a transmission electron microscope image of the nanocrystals in Example 15;
  • Example 3 is a fluorescence emission spectrum diagram of nanocrystals in Example 15.
  • indium precursor indium precursor, and indium precursor all have the same concept
  • phosphorus source, phosphorus precursor, and phosphorus precursor all have the same concept
  • the zinc source, zinc precursor, and zinc precursor are all the same concept.
  • sulfur source, sulfur precursor, and sulfur precursor are all the same concept.
  • Fig. 1 is a schematic structural diagram of indium phosphide nanocrystals prepared in an exemplary embodiment of the present application.
  • the nanocrystal 100 includes a nanocrystal core 101, and the nanocrystal core 101 includes In, P, metal element M, and optional Zn; and a shell 102 disposed on the nanocrystalline core 101.
  • the method for preparing indium phosphide nanocrystals includes the step of using M-(OC ⁇ P) n as one of the reaction precursors, where M is a metal element, and n is the valence of M State, for example, n is 1, 2, or 3.
  • M element is a monovalent metal element such as Li, Na, K, Rb, Cs, etc.
  • n is 1.
  • M element is a divalent metal element such as Zn, Ca, Mn, Sr, etc.
  • n is 2.
  • M element is a trivalent metal element such as Al, Ga, Tl, etc.
  • M-(OC ⁇ P) n is Li-OC ⁇ P, Na-OC ⁇ P, KOC ⁇ P, Zn-(OC ⁇ P) 2 or Ga-(OC ⁇ P) 3 .
  • M-(OC ⁇ P) n can be synthesized according to methods in the prior art.
  • the aforementioned reaction precursors also include indium precursors.
  • the indium precursors are preferably indium halides, such as indium chloride, indium bromide, and indium iodide.
  • the reaction precursor may also include a zinc precursor, and the zinc precursor preferably includes zinc carboxylate.
  • the preparation of indium phosphide nanocrystals includes first preparing an indium phosphide nanocrystal core, and then including a shell layer on the surface of the indium phosphide nanocrystal core.
  • the preparation of indium phosphide nanocrystalline nuclei includes the following steps: high-temperature treatment of the solution containing indium precursor, M-(OC ⁇ P) n and solvent, wherein the temperature of the high-temperature treatment is preferably between 150°C and 300°C, and more Preferably it is between 180°C and 240°C.
  • the solvent is preferably a coordination compound, and the coordination compound includes a carboxylic acid, such as oleic acid, myristic acid, etc.; the coordination compound can also be an amine, such as oleylamine, stearylamine, tetradecylamine, etc.
  • the preparation method of the present invention is the same as the reaction environment required for preparing nanocrystals in the prior art.
  • the inert gas atmosphere includes at least one of nitrogen, argon or rare gas. It should be understood that since the boiling points of the solvents under different pressures are different, the boiling points of the solvents in this application refer to the boiling points under standard atmospheric pressure.
  • This application provides a method for preparing near-infrared indium phosphide nanocrystals, including the steps: S1, obtaining a first solution system containing an indium precursor and an optional zinc precursor, containing M-(OC ⁇ P) n as The second solution system of the phosphorus precursor; where M is a metal element and n is 1, 2 or 3; S2, at a predetermined temperature, the first solution system containing the indium precursor and the second solution containing the phosphorus precursor The system is mixed and reacted to obtain indium phosphide nanocrystals; wherein the first solution system containing the indium precursor includes an indium precursor and a first organic solvent for dispersing the indium precursor, and the second solution system containing the phosphorus precursor includes a phosphorus precursor The first organic solvent is different from the second organic solvent, and the boiling point of the second organic solvent is lower than the predetermined temperature.
  • the boiling point of the second organic solvent is at least 30°C lower than the predetermined temperature.
  • the above-mentioned synthesis method further includes step S3, adding precursor materials required for synthesizing the shell of the nanocrystal into the reaction system of S2, and forming a shell on the surface of the near-infrared indium phosphide nanocrystal to make the near infrared
  • the fluorescence emission peak of infrared indium phosphide nanocrystals is between 700nm and 900nm.
  • the temperature range for mixing and reacting the first solution system containing the indium precursor and the second solution system containing the phosphorus precursor in S2 of the present application is 180-320°C.
  • the boiling point of the organic solvent is 150°C or less, preferably 60 to 150°C.
  • the temperature of the first solution system containing the indium precursor is adjusted to 180-280° C.
  • the second solution system containing the phosphorus precursor is added to obtain an indium-phosphorus mixed solution system;
  • the indium-phosphorus mixed solution system is heated to 280-320°C, kept warm and reacted for a period of time to obtain a solution system containing indium phosphide nanocrystals.
  • the M element is a monovalent metal element such as Li, Na, K, Rb, Cs, etc.
  • n is 1.
  • the M element is a divalent metal element such as Zn, Ca, Mn, Sr, etc.
  • n is 2.
  • the M element is a trivalent metal element such as Al, Ga, Tl, etc.
  • n is 3.
  • the phosphorus precursor M—(O—C ⁇ P) n is Li—O—C ⁇ P, Na—O—C ⁇ P, K—O—C ⁇ P, Zn—(O —C ⁇ P) 2 or Ga—(O—C ⁇ P) 3 .
  • M—(O—C ⁇ P) n is selected as the new phosphorus precursor for the synthesis of indium phosphide nanocrystals.
  • the indium precursor and M—(O—C ⁇ P)n are mixed and reacted at a predetermined temperature, and indium phosphide nanocrystals with a wavelength range of 700-900 nm can be obtained by only one feeding.
  • the phosphorus precursor M—(O—C ⁇ P) n of the present application can also provide metal element M, thereby preparing nanocrystals with alloy cores composed of In, P and metal element M, further optimizing indium phosphide Optical properties of nanocrystals.
  • the second organic solvent includes at least one of benzene, toluene, cyclohexane, n-hexane, n-heptane, n-octane, tetrahydrofuran, and chloroform.
  • the indium precursor is indium halide.
  • the indium precursor includes at least one of indium chloride, indium bromide, and indium iodide.
  • the first organic solvent is at least one of saturated or unsaturated amines with carbon number ⁇ 6.
  • the first organic solvent includes hexylamine, heptylamine, octylamine, trioctylamine, nonylamine, decaamine, decaenamine, undecylamine, undecenamine, dodecylamine, Dienamine, tridecylamine, tridecenamine, tetradecenamine, pentadecenamine, pentadecenamine, hexadecylamine, heptadecylamine, octadecenamine, octadecenamine, oleylamine, decaenamine, At least one of undecenylamine, dodecenylamine, tridecenylamine, tetradecenylamine, pentadecenylamine, hexadecenylamine, heptylamine, octa
  • the first solution system containing the indium precursor also includes a zinc precursor.
  • the zinc precursor includes zinc acetate, zinc chloride, zinc carbonate, zinc decaacid, zinc undecylenate, zinc stearate, zinc oleate, and zinc diethyldithiocarbamate. At least one of.
  • a shell layer is coated on the indium phosphide nanocrystal.
  • the precursor material required for the synthesis of the shell layer is added to the solution system containing the nanocrystals to obtain the indium phosphide nanocrystals covering the shell layer.
  • the precursor material required for the synthesis of the shell layer includes a zinc precursor, and at least one of a sulfur precursor and a selenium precursor.
  • the step of removing unreacted raw materials and other impurities is further included, which specifically includes Separation and purification. These steps are well-known methods in the art, and will not be repeated here.
  • an indium phosphide nanocrystal is provided, which is prepared by the above preparation method, and the emission peak of the indium phosphide nanocrystal is above 700 nm, preferably 700 to 900 nm.
  • indium phosphide nanocrystals In the prior art, in order to obtain large-wavelength indium phosphide nanocrystals, a method of increasing the size of indium phosphide nanocrystals is often used. However, this method often causes problems such as increased surface defects and difficulty in wavelength control, and cannot meet application requirements.
  • the preparation method of the present application can directly obtain indium phosphide nanocrystals with an emission wavelength of 700-900 nm through only a one-step method.
  • indium phosphide nanocrystals contain M, In and P elements, where M is a metal element.
  • M is a metal element.
  • the constituent elements of the indium phosphide nanocrystals further include Zn, but the constituent elements of the indium phosphide nanocrystals of the present invention are not limited thereto.
  • the indium phosphide nanocrystal is coated with a shell layer, wherein the shell layer contains Zn element and at least one of S element and Se element.
  • the shell layer is at least one of ZnS, ZnSe and ZnSeS.
  • the present application provides a method for preparing red light indium phosphide nanocrystals, which includes the steps of: S1, mixing an indium precursor, a phosphorus precursor, and an organic solvent, reacting at a first temperature and holding for a period of time to obtain indium phosphide Nanocrystalline nucleus solution; S2, the indium phosphide nanocrystalline nucleus solution is rapidly heated to the second temperature and kept for a period of time; S3, the precursor material required for the synthesis of the nanocrystalline shell is added to the reaction system of S2 to obtain red
  • the light indium phosphide nanocrystal has a fluorescence emission peak value of 580-670 nm.
  • the first temperature is in the range of 110 to 160°C
  • the second temperature is preferably in the range of 280 to 340°C.
  • the indium phosphide nanocrystal nucleus solution is rapidly heated to the second temperature and maintained for at least 10 minutes.
  • the time required for the indium phosphide nanocrystal nucleus solution to rapidly rise to the second temperature is controlled within 10 minutes.
  • the inventor found that adjusting the temperature of the reaction system from the first temperature to the second temperature within the above-mentioned "rapidly heating up" time range is conducive to the rapid aggregation and growth of indium phosphide nanocrystal nuclei, thereby obtaining nanocrystals with uniform particle size. .
  • the preparation method of indium phosphide nanocrystals widely used in the prior art is usually a high-temperature injection method, so that the indium precursor and the phosphorus precursor directly nucleate and grow mature directly at high temperature, and then coat the shell layer as needed to prepare Nanocrystals with a wavelength range of 520-720nm are produced.
  • the high-temperature injection method is difficult to balance the nucleation and growth processes of the nanocrystals, which makes the size distribution of the prepared nanocrystals uneven and the half-value width becomes wider.
  • the temperature at which the indium precursor, the phosphorus precursor, and the organic solvent are mixed and reacted is 120 to 160°C.
  • the lower first temperature can also effectively avoid the risk of oxidation of the surface of the indium phosphide nanocrystalline nucleus, which is more conducive to the growth process of free monomer reactants on the surface of the seed crystal, so that the prepared indium phosphide nanocrystalline Crystal has better optical properties.
  • the above-mentioned indium phosphide nanocrystalline nucleus solution is rapidly heated to 280-320° C. and kept for a period of at least 10 minutes.
  • the inventor found that at the higher second temperature, the indium phosphide nanocrystalline nuclei further aggregate and grow, and the particle size of the indium phosphide nanocrystalline nucleus in the system gradually becomes larger, thereby realizing the growth of the indium phosphide nanocrystalline nucleus "Maturation process".
  • the precursor materials required for the shell synthesis are added to the above-mentioned mixed system containing indium phosphide nanocrystal cores to realize the shell coating process of the nanocrystals, and finally obtain the red light phosphating with shell coating Indium nanocrystals.
  • This application adopts the technical means of "low temperature nucleation-rapid heating to assist nucleus growth-final cladding".
  • indium phosphide nanocrystalline nuclei are prepared at a lower first temperature, and then the nanocrystalline nucleus is controlled by means of rapid heating. Further aggregation and growth, and finally a nanocrystalline shell is formed on the surface of the nanocrystalline core.
  • the reaction temperature controls the reaction temperature, the nucleation, growth and coating processes of indium phosphide nanocrystalline are effectively balanced, and a core-shell structure is obtained.
  • the organic solvent is selected from at least one of saturated or unsaturated amines with carbon number ⁇ 6.
  • the organic solvent is selected from at least one of primary amines and secondary amines.
  • the organic solvent is selected from hexaamine, heptylamine, octylamine, nonylamine, decaamine, decaenamine, undecylamine, undecenamine, dodecylamine, dodecenamine, tridecylamine Amine, tridecenamine, tetradecenamine, tetradecenamine, pentadecenamine, pentadecenamine, hexadecylamine, hexadecenamine, heptadecenamine, heptadecenamine, octadecenamine and octadecene At least one of amines.
  • the chemical structural formula of the phosphorus precursor is M—(O—C ⁇ P) n , where M is a metal element, and n is 1, 2 or 3.
  • M is a metal element
  • n is 1, 2 or 3.
  • M element is a monovalent metal element such as Li, Na, K, Rb, Cs, etc.
  • n is 1.
  • the M element is a divalent metal element such as Zn, Ca, Mn, Sr, etc.
  • n is 2.
  • the M element is a trivalent metal element such as Al, Ga, Tl, etc., n is 3.
  • the phosphorus precursor M—(O—C ⁇ P) n can provide the metal element M, and prepare nanocrystals with an alloy core composed of In, P and the metal element M, so as to further optimize Optical properties of indium phosphide nanocrystals.
  • the phosphorus precursor M—(O—C ⁇ P) n is Li—O—C ⁇ P, Na—O—C ⁇ P, K—O—C ⁇ P, Zn—(O —C ⁇ P) 2 or Ga—(O—C ⁇ P) 3 .
  • the indium phosphide nanocrystal nucleus solution contains the first zinc precursor.
  • the first zinc precursor is selected from zinc halides.
  • the first zinc precursor is selected from at least one of zinc chloride, zinc bromide, and zinc iodide.
  • the ratio of the first zinc precursor to the indium precursor is (0.01-10):1 based on the amount of the substance. In a specific embodiment, the ratio of the first zinc precursor to the indium precursor is (0.1-1):1 based on the amount of the substance.
  • the shell of the nanocrystal includes at least one of ZnS, ZnSe, and ZnSeS.
  • the shell of the nanocrystal includes at least two shells, wherein the at least two shells are adjacent and different from each other.
  • the shell of the nanocrystal includes two shells, wherein the shell far from the indium phosphide nanocrystalline core is ZnS, and the shell near the indium phosphide nanocrystalline core is ZnSe or ZnSeS.
  • the precursor material required to synthesize the shell of the nanocrystal includes a second zinc precursor and at least one of a sulfur precursor and a selenium precursor.
  • the second zinc precursor is selected from zinc carboxylate, or organozinc reagent (a reagent in which zinc is directly connected to an alkyl group).
  • the second zinc precursor is selected from zinc acetate, zinc stearate, zinc oleate, zinc decaacid, zinc undecylenate, zinc myristate, zinc palmitate, zinc diethyldithiocarbamate At least one of medium and diethyl zinc.
  • the sulfur precursor is selected from at least one of alkyl mercaptans and a solution formed by dissolving elemental sulfur in a solvent.
  • the sulfur precursor is selected from at least one of alkyl mercaptan, trialkyl phosphine sulfide, trienyl phosphine sulfide, and organic amine solution of sulfur. More preferably, the sulfur precursor is selected from at least one of tri-n-butyl phosphine sulfide, trioctyl phosphine sulfide, and sulfur oleyl amine solution.
  • the selenium precursor is selected from a solution formed by dissolving elemental selenium in a solvent.
  • the selenium precursor is selected from at least one of trialkyl phosphine selenide, trienyl phosphine selenide, and organic amine solution of selenium. Further preferably, the selenium precursor is selected from at least one of tri-n-butyl phosphine selenide, trioctyl phosphine selenide, and an oleylamine solution of selenium.
  • the inventor found that the above-mentioned zinc precursors, sulfur precursors, and selenium precursors have relatively high reactivity, which is beneficial for coating the indium phosphide nanocrystalline core with a high-quality shell layer.
  • Using the above-mentioned zinc precursor, sulfur precursor, and selenium precursor as the precursor materials required for the synthesis of the nanocrystalline shell can make the growth of the nanocrystalline shell more uniform, thereby effectively improving the fluorescence quantum yield of the indium phosphide nanocrystalline rate.
  • the method for preparing red light indium phosphide nanocrystals further includes the steps of: S4, continuing to increase the temperature, and adding precursor materials required for the synthesis of the nanocrystal shell again into the reaction system of S3 to obtain
  • the red light indium phosphide nanocrystal has a fluorescence emission peak at 580-670 nm.
  • the inventor found that coating the shell layer with the indium phosphide nanocrystal core multiple times and repeatedly according to actual needs can make the shell layer better and more uniformly cover the surface of the indium phosphide nanocrystal core. Thereby, the luminous efficiency and photochemical stability of indium phosphide nanocrystals are further improved.
  • the step of removing unreacted raw materials and other impurities is further included, which specifically includes Separation and purification. These steps are well-known methods in the art, and will not be repeated here.
  • a red light indium phosphide nanocrystal which is prepared by the following steps: S1, mixing an indium precursor, a phosphorus precursor and an organic solvent, React at the first temperature to obtain the indium phosphide nanocrystalline nucleus solution; S2, rapidly heat the indium phosphide nanocrystalline nucleus solution to the second temperature and keep it for a period of time; S3, add the synthetic nanocrystalline nucleus to the reaction system of S2
  • the precursor material required for the shell is used to obtain red light indium phosphide nanocrystals, and the fluorescence emission peak of the red light indium phosphide nanocrystals is 580-670 nm.
  • the first temperature ranges from 110°C to 160°C.
  • the range of the second temperature is 280 to 340°C.
  • the indium phosphide nanocrystal nucleus solution is rapidly heated to the second temperature and maintained for at least 10 minutes.
  • the organic solvent is selected from at least one of saturated or unsaturated amines with carbon number ⁇ 6. According to a preferred embodiment of the present application, the organic solvent is selected from at least one of primary amines and secondary amines.
  • the organic solvent is selected from hexaamine, heptylamine, octylamine, nonylamine, decaamine, decaenamine, undecylamine, undecenamine, dodecylamine, dodecenamine, tridecylamine Amine, tridecenamine, tetradecenamine, tetradecenamine, pentadecenamine, pentadecenamine, hexadecylamine, hexadecenamine, heptadecenamine, heptadecenamine, octadecenamine and octadecene At least one of amines.
  • the chemical structural formula of the phosphorus precursor is M—(O—C ⁇ P) n , where M is a metal element, and n is 1, 2 or 3.
  • M is a metal element
  • n is 1, 2 or 3.
  • M element is a monovalent metal element such as Li, Na, K, Rb, Cs, etc.
  • n is 1.
  • the M element is a divalent metal element such as Zn, Ca, Mn, Sr, etc.
  • n is 2.
  • the M element is a trivalent metal element such as Al, Ga, Tl, etc., n is 3.
  • the phosphorus precursor M—(O—C ⁇ P) n is Li—O—C ⁇ P, Na—O—C ⁇ P, K—O—C ⁇ P, Zn—(O —C ⁇ P) 2 or Ga—(O—C ⁇ P) 3 .
  • the indium phosphide nanocrystal nucleus solution contains the first zinc precursor.
  • the first zinc precursor is selected from zinc halides.
  • the first zinc precursor is selected from at least one of zinc chloride, zinc bromide, and zinc iodide.
  • the ratio of the first zinc precursor to the indium precursor is (0.01-10):1 based on the amount of the substance. In a specific embodiment, the ratio of the first zinc precursor to the indium precursor is (0.1-1):1 based on the amount of the substance.
  • the shell of the nanocrystal includes at least one of ZnS, ZnSe, and ZnSeS.
  • the shell of the nanocrystal includes at least two shells, wherein the at least two shells are adjacent and different from each other.
  • the shell of the nanocrystal includes two shells, wherein the shell far from the indium phosphide nanocrystalline core is ZnS, and the shell near the indium phosphide nanocrystalline core is ZnSe or ZnSeS.
  • the red light indium phosphide nanocrystals can also be prepared by the following steps: S1, mixing the indium precursor, the phosphorus precursor and the organic solvent, and reacting at the first temperature to obtain phosphorus Indium phosphide nanocrystalline core solution; S2, the indium phosphide nanocrystalline core solution is rapidly heated to the second temperature, and maintained for a period of time; S3, the precursor material required for the synthesis of the nanocrystalline shell is added to the reaction system of S2 S4, continue to heat up, and again add the precursor material required to synthesize the shell of the nanocrystal in the reaction system of S3 to obtain red light indium phosphide nanocrystals.
  • the fluorescence emission peak of the red light indium phosphide nanocrystals is at 580 ⁇ 670nm.
  • the inventor found that the indium phosphide nanocrystals have excellent luminescence performance, a small half-width of the fluorescence emission peak ( ⁇ 50nm), and a high fluorescence quantum yield (>80%).
  • the red indium phosphide synthesized in the prior art tends to have a large half-peak width, low quantum yield and poor stability.
  • the core is doped with M element, which improves the quantum yield; the two-step temperature control reduces the half-peak width, so that the synthesized product has better performance.
  • This application provides a method for preparing cyan indium phosphide nanocrystals, which includes the steps of: S1, mixing an indium precursor, an optional zinc precursor, and a phosphorus precursor M-(OC ⁇ P) n with an organic solvent, React at a first temperature to obtain an indium phosphide nanocrystalline nucleus solution; S2, at the first temperature, add a cation precursor of zinc to the indium phosphide nanocrystalline nucleus solution to form a first mixed solution; S3, a second temperature Next, adding sulfur or selenium anion precursor to the first mixed solution, the cation precursor and the anion precursor react to form an indium phosphide nanocrystal core coating shell layer to obtain cyan indium phosphide nanocrystals.
  • the fluorescence emission peak of indium nanocrystals is 460-500nm; wherein, the second temperature is greater than the first temperature.
  • the solution system containing the indium precursor and the phosphorus precursor is first heated to 110-160°C, and after holding for a period of time, the cation precursor of zinc is added, wherein the cation precursor of zinc is the same as step S1
  • the ratio of the indium precursor described in is (8-40):1.
  • the temperature is raised to the second reaction temperature of 160-240°C, and sulfur or selenium anion precursors are added in an equimolar amount with zinc to obtain a solution system containing indium phosphide nanocrystals.
  • the first temperature ranges from 110°C to 160°C.
  • the range of the second temperature is 160 to 200°C.
  • the organic solvent is selected from at least one of saturated or unsaturated amines with carbon number ⁇ 6 or carboxylic acids.
  • the organic solvent is selected from hexaamine, heptylamine, octylamine, nonylamine, decaamine, decaenamine, undecylamine, undecenamine, dodecylamine, dodecenamine, tridecylamine Amine, tridecenamine, tetradecenamine, tetradecenamine, pentadecenamine, pentadecenamine, hexadecylamine, hexadecenamine, heptadecenamine, heptadecenamine, octadecenamine and octadecene At least one of amines.
  • the chemical structural formula of the phosphorus precursor is M—(O—C ⁇ P) n , where M is a metal element, and n is the valence state of the M element, for example, n is 1, 2 Or 3.
  • the phosphorus precursor M—(O—C ⁇ P) n is Li—O—C ⁇ P, Na—O—C ⁇ P, K—O—C ⁇ P, Zn—(O —C ⁇ P) 2 or Ga—(O—C ⁇ P) 3 .
  • M—(O—C ⁇ P) n is selected as the new phosphorus precursor for the synthesis of indium phosphide nanocrystals.
  • the indium precursor and M—(O—C ⁇ P)n are mixed and heated to the first temperature to react to obtain the final indium phosphide nanocrystal solution, and then the shell layer is rapidly coated.
  • the phosphorus precursor M—(O—C ⁇ P) n of the present application can also provide metal element M, thereby preparing nanocrystals with alloy cores composed of In, P and metal element M, further optimizing indium phosphide Optical properties of nanocrystals.
  • the indium phosphide nanocrystal nucleus solution may optionally contain a first zinc precursor, and the first zinc precursor is selected from zinc halides.
  • the first zinc precursor is selected from at least one of zinc chloride, zinc bromide, and zinc iodide.
  • the zinc source includes zinc acetate, zinc chloride, zinc carbonate, zinc decaacid, zinc undecylenate, zinc stearate, zinc oleate, and zinc diethyldithiocarbamate. At least one. The inventor found that in the process of preparing indium phosphide nanocrystalline nuclei, introducing a certain amount of zinc precursor into the reaction system can further reduce the surface defects of the nanocrystalline nucleus and enhance the energy-level luminous efficiency of the nanocrystalline.
  • the ratio of the first zinc precursor to the indium precursor is (3-20):1 based on the amount of the substance. In a specific embodiment, the ratio of the first zinc precursor to the indium precursor is (3-10):1 based on the amount of the substance.
  • the ratio of the cation precursor of zinc in step S2 to the indium precursor in step S1 is (8-40):1 based on the amount of substance.
  • the ratio of the cation precursor of zinc in step S2 to the indium precursor in step S1 is (10-20):1 based on the amount of substance.
  • the cationic precursor is a second zinc precursor.
  • the second zinc precursor is selected from organozinc reagents.
  • the second zinc precursor is selected from zinc acetate, zinc stearate, zinc oleate, zinc tenate, zinc undecylenate, zinc myristate, zinc palmitate, diethyl At least one of zinc.
  • the anion precursor is at least one of a sulfur precursor and a selenium precursor.
  • the sulfur precursor is selected from at least one of alkyl mercaptan and a solution formed by dissolving elemental sulfur in a solvent.
  • the sulfur precursor is selected from at least one of alkyl mercaptan, trialkyl phosphine sulfide, trienyl phosphine sulfide, and sulfur organic amine solution.
  • the sulfur precursor is selected from at least one of tri-n-butyl phosphine sulfide, trioctyl phosphine sulfide, and an oleyl amine solution of sulfur.
  • the selenium precursor is selected from a solution formed by dissolving elemental selenium in a solvent.
  • the selenium precursor is selected from at least one of trialkylphosphine selenide, trienyl phosphine selenide, and organic amine solutions of selenium.
  • the selenium precursor is selected from at least one of tri-n-butyl phosphine selenide, trioctyl phosphine selenide, and an oleylamine solution of selenium.
  • the inventor found that the above-mentioned sulfur precursors and selenium precursors have relatively high reactivity, which is beneficial for coating the indium phosphide nanocrystalline core with a high-quality shell layer.
  • Using the above-mentioned sulfur precursor and selenium precursor as the anion precursor can make the growth of the shell layer of the nanocrystal more uniform, thereby effectively improving the fluorescence quantum yield of the indium phosphide nanocrystal.
  • the method for preparing cyan indium phosphide nanocrystals further includes the step of: S4, adding a cation precursor and an anion precursor to the reaction system in step S3 to obtain cyan indium phosphide nanocrystals.
  • the fluorescence emission peak of the cyan indium phosphide nanocrystal is 460-500nm.
  • the inventor found that coating the shell layer with the indium phosphide nanocrystal core multiple times and repeatedly according to actual needs can make the shell layer better and more uniformly cover the surface of the indium phosphide nanocrystal core. Thereby, the luminous efficiency and photochemical stability of indium phosphide nanocrystals are further improved.
  • S4 is carried out under gradually increasing the temperature of the reaction system.
  • the step of removing unreacted raw materials and other impurities is further included, which specifically includes Separation and purification. These steps are well-known methods in the art, and will not be repeated here.
  • a cyan indium phosphide nanocrystal is provided, the cyan indium phosphide nanocrystal is prepared by the following steps: S1, mixing an indium precursor, a phosphorus precursor and an organic solvent, React at the first temperature to obtain an indium phosphide nanocrystalline nucleus solution; S2, at the first temperature, add a cationic precursor to the indium phosphide nanocrystalline nucleus solution to form a first mixed solution; S3, at the second temperature, An anion precursor is added to the first mixed solution, and the cation precursor reacts with the anion precursor to form an indium phosphide nanocrystalline core coating shell layer to obtain cyan indium phosphide nanocrystals.
  • the fluorescence of the cyan indium phosphide nanocrystals is The emission peak-to-peak value is 460-500nm; wherein, the second temperature is greater than the first temperature.
  • the first temperature ranges from 110°C to 160°C.
  • the range of the second temperature is 160 to 200°C.
  • the organic solvent is selected from at least one of saturated or unsaturated amines with carbon number ⁇ 6.
  • the organic solvent is selected from hexaamine, heptylamine, octylamine, nonylamine, decaamine, decaenamine, undecylamine, undecenamine, dodecylamine, dodecenamine, tridecylamine Amine, tridecenamine, tetradecenamine, tetradecenamine, pentadecenamine, pentadecenamine, hexadecylamine, hexadecenamine, heptadecenamine, heptadecenamine, octadecenamine and octadecene At least one of amines.
  • the chemical structural formula of the phosphorus precursor is M—(O—C ⁇ P) n , where M is a metal element, and n is the valence state of the M element, for example, n is 1, 2 Or 3.
  • M element is a monovalent metal element such as Li, Na, K, Rb, Cs, etc.
  • n is 1.
  • the M element is a divalent metal element such as Zn, Ca, Mn, Sr, etc.
  • n is 2.
  • the M element is a trivalent metal element such as Al, Ga, Tl, etc., n is 3.
  • the phosphorus precursor M—(O—C ⁇ P) n is Li—O—C ⁇ P, Na—O—C ⁇ P, K—O—C ⁇ P, Zn—(O —C ⁇ P) 2 or Ga—(O—C ⁇ P) 3 .
  • the indium phosphide nanocrystal nucleus solution contains the first zinc precursor.
  • the first zinc precursor is selected from zinc halides.
  • the first zinc precursor is selected from at least one of zinc chloride, zinc bromide, and zinc iodide.
  • the ratio of the first zinc precursor to the indium precursor is (3-20):1 based on the amount of the substance. In a specific embodiment, the ratio of the first zinc precursor to the indium precursor is (3-10):1 based on the amount of the substance. According to a preferred embodiment of the present application, the ratio of the cation precursor in step S2 to the indium precursor in step S1 is (8-40):1 based on the amount of substance. In a specific embodiment, the ratio of the cation precursor in step S2 to the indium precursor in step S1 is (10-20):1 based on the amount of substance.
  • the cationic precursor is a second zinc precursor.
  • the second zinc precursor is selected from zinc carboxylate or organic zinc reagent.
  • the second zinc precursor is selected from zinc acetate, zinc stearate, zinc oleate, zinc tenate, zinc undecylenate, zinc myristate, zinc palmitate, diethyl At least one of zinc.
  • the anion precursor is at least one of a sulfur precursor and a selenium precursor.
  • the sulfur precursor is selected from at least one of alkyl mercaptan and a solution formed by dissolving elemental sulfur in a solvent.
  • the sulfur precursor is selected from at least one of alkyl mercaptan, trialkyl phosphine sulfide, trienyl phosphine sulfide, and sulfur organic amine solution.
  • the sulfur precursor is selected from at least one of tri-n-butyl phosphine sulfide, trioctyl phosphine sulfide, and an oleyl amine solution of sulfur.
  • the selenium precursor is selected from a solution formed by dissolving elemental selenium in a solvent.
  • the selenium precursor is selected from at least one of trialkylphosphine selenide, trienyl phosphine selenide, and organic amine solutions of selenium.
  • the selenium precursor is selected from at least one of tri-n-butyl phosphine selenide, trioctyl phosphine selenide, and an oleylamine solution of selenium.
  • the cyan indium phosphide nanocrystal can also be prepared by the following steps: S1, mixing the indium precursor, the phosphorus precursor and the organic solvent, and reacting at the first temperature to obtain phosphorus Indium phosphate nanocrystalline nucleus solution; S2, at the first temperature, add cationic precursors to the indium phosphide nanocrystalline nucleus solution to form a first mixed solution; S3, at the second temperature, before adding anions to the first mixed solution The cation precursor and the anion precursor react to form the indium phosphide nanocrystal core coating shell; S4, adding the cation precursor and the anion precursor to the reaction system of step S3 again to obtain the cyan light indium phosphide nanocrystal; Wherein, the second temperature is greater than the first temperature.
  • the fluorescence emission peak of the indium phosphide nanocrystal is 460-500 nm.
  • the inventor found that the fluorescence quantum yield of the indium phosphide nanocrystals is high (>50%), thereby broadening the application range of the indium phosphide nanocrystals.
  • the synthesis method of cyan indium phosphide is limited, and the performance of the synthesized product is not good.
  • the synthesis of cyan indium phosphide becomes simple and efficient. Due to the doping of M element, the wavelength of the disc synthesized by this method is controllable, the efficiency is high, and the half-peak width is narrow.
  • the indium phosphide nanocrystal 1 is composed of three elements, In, P, and Na, and the shell is a double shell layer composed of ZnSe and ZnS.
  • the second solvent is toluene.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 280° C. and reacting for 60 min to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 1 is obtained after separation and purification.
  • the indium phosphide nanocrystal 2 is composed of four elements: In, P, Na, and Zn, and the shell is a double shell layer composed of ZnSe and ZnS.
  • the second solvent is toluene.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 280° C. and reacting for 60 min to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 2 is obtained after separation and purification.
  • Indium phosphide nanocrystal 3 is composed of four elements: In, P, K, and Zn, and the shell is a double shell layer composed of ZnSe and ZnS.
  • the second solvent is toluene.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 280° C. and reacting for 60 min to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 3 is obtained after separation and purification.
  • the indium phosphide nanocrystal 4 is composed of three elements of In, P, and K, and the shell is a double shell layer composed of ZnSe and ZnS.
  • the second solvent is toluene.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 300° C. and reacting for 60 minutes to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 4 is obtained after separation and purification.
  • the indium phosphide nanocrystal 5 is composed of three elements: In, P, and Na, and the second solvent is n-heptane.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 280° C. and reacting for 60 min to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 6 is composed of three elements: In, P, and Na, the second solvent is toluene, and it is nucleated at 240°C.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 280° C. and reacting for 60 min to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 7 is composed of In, P, and Na three elements, and the shell is a double shell layer composed of ZnSe and ZnS.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 300° C. and reacting for 60 minutes to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 7 is obtained after separation and purification.
  • the indium phosphide nanocrystal 8 is composed of three elements of In, Zn, and P, and the shell is a double shell layer composed of ZnSe and ZnS.
  • Indium phosphide nanocrystal 9 is composed of three elements: In, P, and Na.
  • step S3 heating the indium-phosphorus mixed solution system of step S2 to 280° C. and reacting for 60 min to obtain a solution system containing indium phosphide nanocrystals;
  • the indium phosphide nanocrystal 10 is composed of three elements: In, Zn, and P.
  • the first solution system containing the indium precursor and the second solution system containing the phosphorus precursor are mixed and reacted at a predetermined temperature, and the boiling point of the second organic solvent is lower than the predetermined temperature.
  • temperature indium phosphide nanocrystals with a wavelength range of 700 to 900 nm can be directly obtained in one step with only one feeding, which realizes the application of indium phosphide nanocrystals in the near-infrared wavelength range, thereby broadening the indium phosphide nanocrystals Application scope.
  • indium phosphide nanocrystalline nuclei heat the indium phosphide nanocrystalline nucleus solution of S1 to 300°C for 10 minutes and keep it for 30 minutes;
  • S3 Indium phosphide nanocrystalline core coating shell layer: Add 10 mmol zinc acetate and 10 mmol sulfur oleylamine solution to the reaction system of S2, and react for 60 minutes to obtain red light indium phosphide nanocrystal 11.
  • S3 Indium phosphide nanocrystalline core coating shell layer: Add 10 mmol zinc acetate and 10 mmol sulfur oleylamine solution to the reaction system of S2, and react for 60 minutes to obtain red light indium phosphide nanocrystal 12.
  • S3 Indium phosphide nanocrystalline core coating shell layer: Add 10 mmol zinc acetate and 10 mmol sulfur oleylamine solution to the reaction system of S2, and react for 60 minutes to obtain red light indium phosphide nanocrystal 13.
  • indium phosphide nanocrystalline nuclei heat the indium phosphide nanocrystalline nucleus solution of S1 to 300°C for 10 minutes and keep it for 30 minutes;
  • the indium phosphide nanocrystal 14 is obtained after separation and purification.
  • indium phosphide nanocrystalline nuclei heat the indium phosphide nanocrystalline nucleus solution of S1 to 320°C for 10 minutes and keep it for 30 minutes;
  • S2 is the indium phosphide nanocrystal core coating shell layer: add 6mmol zinc stearate octadecene solution to the indium phosphide nanocrystal core solution of S1, and then add 6mmol trioctylphosphine sulfide solution, and react for 60min, Obtain indium phosphide nanocrystal 19.
  • the indium phosphide nanocrystal 21 is obtained after separation and purification.
  • Test characterization The red light indium phosphide nanocrystals obtained in Example 7 to Example 14 and the indium phosphide nanocrystals obtained in Comparative Example 5 to Comparative Example 7 were dispersed in a toluene solution, and the fluorescence spectrum and fluorescence quantum were tested. Yield. The specific test results are shown in the table below.
  • the indium phosphide nanocrystals of the present application have a smaller half-width of the fluorescence emission peak and higher fluorescence quantum yield, which proves that the indium phosphide nanocrystals obtained by the preparation method of the present application have excellent properties. Luminous performance, thereby broadening the application range of indium phosphide nanocrystals.
  • the indium phosphide nanocrystalline core is composed of In, P, and Li three elements, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of three elements: In, P and Na, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of In, P, and Zn three elements, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of three elements: In, P, and Ga, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of four elements: In, P, Na and Zn, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of In, P, and Li three elements, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of three elements: In, P and Na, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of In, P, and Zn three elements, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of three elements: In, P, and Ga, and the shell is a double shell layer composed of ZnSe and ZnS.
  • nanocrystals are obtained after separation and purification.
  • Example 2 is a transmission electron microscope image of the indium phosphide nanocrystals prepared in Example 15. It can be seen from the figure that the size of the indium phosphide nanocrystals is about 3.5 nm.
  • Example 3 is a fluorescence emission spectrum diagram of indium phosphide nanocrystals in Example 15.
  • the peak-to-peak fluorescence emission wavelength is about 527 nm, and the half-value width is about 37 nm.
  • Example 15 to Example 19 the fluorescence properties of the indium phosphide nanocrystals in Example 15 to Example 19 and Comparative Example 8 to Comparative Example 11 were further tested.
  • the test results are shown in the following table:
  • Example 15 For example, compared with Comparative Example 8, the half-peak width of Example 15 is reduced by 6 nanometers, and the quantum yield is increased by 20%; Compared with Comparative Example 9, the half-value width of Example 16 is reduced by 7 nm and the quantum yield is increased by 35%; compared with Comparative Example 10, the half-value width of Example 17 is reduced by 6 nm and the quantum yield is increased by 31%; Compared with Comparative Example 11, Example 18 has a half-value width reduced by 6 nanometers and a quantum yield increased by 39%.
  • S2 is the indium phosphide nanocrystalline core coating shell layer: S2-1, at 120°C, add 10 mmol zinc stearate to the indium phosphide nanocrystalline core solution of step S1, and react for 30 minutes to form a first mixed solution; S2-2. The temperature is raised to 160° C., and 10 mmol sulfur oleylamine solution is added to the first mixed solution of step S2-1, and reacted for 60 minutes to obtain cyan light indium phosphide nanocrystal 1.
  • S2 is the indium phosphide nanocrystalline core coating shell layer: S2-1, at 120°C, add 8 mmol zinc stearate to the indium phosphide nanocrystalline core solution of step S1, and react for 30 minutes to form a first mixed solution; S2-2.
  • S2 is the indium phosphide nanocrystalline core coating shell layer: S2-1, at 120°C, add 12 mmol of diethyl zinc to the indium phosphide nanocrystalline core solution of step S1, and react for 30 minutes to form a first mixed solution; S2-2.
  • step S2-1 Raise the temperature to 160°C, add 12mmol of selenium oleylamine solution to the first mixed solution of step S2-1, and react for 30 minutes to form a second mixed solution; S2-3, raise the temperature to 180°C, in step S2- Add 6mmol zinc oleate to the second mixture of 2 and then add 6mmol n-dodecanethiol to react for 60min; S2-4, gradually increase the temperature of the reaction system, and perform three ZnS shell growth to obtain cyan light indium phosphide Nanocrystalline 3.
  • the indium phosphide nanocrystalline core is composed of three elements: In, P, and Na, and the first shell layer is ZnS.
  • S2 is the indium phosphide nanocrystalline core coating shell layer: S2-1, at 120°C, add 10 mmol zinc stearate to the indium phosphide nanocrystalline core solution of step S1, and react for 30 minutes to form a first mixed solution; S2-2. The temperature is raised to 160° C., 10 mmol sulfur oleylamine solution is added to the first mixed solution of step S2-1, and reacted for 60 minutes to obtain cyan indium phosphide nanocrystals.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of In, P and K three elements, and the first shell layer is ZnS.
  • S2 is the indium phosphide nanocrystalline core coating shell layer: S2-1, at 120°C, add 10 mmol zinc stearate to the indium phosphide nanocrystalline core solution of step S1, and react for 30 minutes to form a first mixed solution; S2-2. The temperature is raised to 160° C., and 10 mmol sulfur oleylamine solution is added to the first mixed solution of step S2-1, and reacted for 60 minutes to obtain cyan light indium phosphide nanocrystal 1.
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of three elements: In, P, and Na, and the first shell layer is ZnSeS.
  • S2 is the indium phosphide nanocrystalline core coating shell layer: S2-1, at 120°C, add 8 mmol zinc stearate to the indium phosphide nanocrystalline core solution of step S1, and react for 30 minutes to form a first mixed solution; S2-2. Raise the temperature to 160°C, add 4mmol of trioctylphosphine selenide solution and 4mmol of trioctylphosphine sulfide solution to the first mixed solution of step S2-1, and react for 30 minutes to form a second mixed solution;
  • step S3 Raise the temperature to 240°C, add 6 mmol zinc acetate and then 6 mmol n-dodecanethiol to the second mixed solution of step S2-2, and react for 60 min;
  • nanocrystals are obtained after separation and purification.
  • the indium phosphide nanocrystalline core is composed of In, P, and K, and the first shell layer is ZnSeS.
  • S2 is the indium phosphide nanocrystalline core coating shell layer: S2-1, at 120°C, add 8 mmol zinc stearate to the indium phosphide nanocrystalline core solution of step S1, and react for 30 minutes to form a first mixed solution; S2-2. Raise the temperature to 160°C, add 4mmol of trioctylphosphine selenide solution and 4mmol of trioctylphosphine sulfide solution to the first mixed solution of step S2-1, and react for 30 minutes to form a second mixed solution;
  • step S3 Raise the temperature to 240°C, add 6 mmol zinc acetate and then 6 mmol n-dodecanethiol to the second mixed solution of step S2-2, and react for 60 min;
  • nanocrystals are obtained after separation and purification.
  • S2 is the indium phosphide nanocrystal core coating shell layer: at 240°C, add 6mmol zinc stearate octadecene solution to the indium phosphide nanocrystal core solution of step S1, and then add 6mmol trioctyl sulfide Phosphine solution, react for 60 min.
  • the nanocrystal 30 is obtained after separation and purification.
  • S2 is the indium phosphide nanocrystal core coating shell layer: at 240°C, add 6mmol zinc stearate octadecene solution to the indium phosphide nanocrystal core solution of step S1, and then add 6mmol trioctyl sulfide Phosphine solution, react for 60 min.
  • the nanocrystal 31 is obtained after separation and purification.
  • S2 is the indium phosphide nanocrystal core coating shell layer: at 240°C, add 6mmol zinc stearate octadecene solution to the indium phosphide nanocrystal core solution of step S1, and then add 6mmol trioctyl sulfide Phosphine solution, react for 60 min.
  • nanocrystals are obtained after separation and purification.
  • Test characterization The cyan indium phosphide nanocrystals obtained in Example 20 to Example 26, and the indium phosphide nanocrystals obtained in Comparative Example 12 to Comparative Example 14 were dispersed in a toluene solution, and the fluorescence spectrum and fluorescence quantum were tested. Yield. The specific test results are shown in the table below.
  • this application can successfully prepare cyan indium phosphide nanocrystals with high fluorescence quantum yield, which proves that the cyan indium phosphide nanocrystals obtained by the preparation method of this application have excellent luminescence properties, thereby broadening
  • the application scope of indium phosphide nanocrystals is discussed.

Abstract

本申请公开了一种利用新型磷前驱体为原料制备磷化铟纳米晶的方法及以此方法制备的不同波长的磷化铟纳米晶。磷化铟纳米晶的制备方法包括步骤：采用M-(O-C≡P)n作为反应前驱体之一，其中，M为金属元素，n为M元素的化合价价态值。本申请采用M-(O-C≡P)n作为反应前驱体之一，由于金属元素M与P元素来自同一反应前驱体，能制备含有In、P和金属元素M的纳米晶核的纳米晶。

Description

利用新型磷前驱体制备磷化铟纳米晶的方法及其制备的磷化铟纳米晶 技术领域
本申请属于纳米材料领域，尤其涉及一种利用新型磷前驱体为原料制备磷化铟纳米晶的方法及以此方法制备的不同波长的磷化铟纳米晶。
背景技术
相比有机荧光染料，纳米晶具有抗光漂白、量子产率高，半峰宽窄等优点，在显示、照明和生物成像领域有着巨大的应用前景。然而，现有技术研究和应用最多的II-VI族元素量子点(硒化镉、碲化镉等)含有镉等高毒性元素，具有明显的神经毒性，限制此类量子点的应用。
与II-VI族元素量子点相比，以磷化铟量子点为代表的III-V族元素量子点不具有内在的毒性、应用范围更广，正逐渐受到科研界和产业界的关注。然而，现有技术合成的磷化铟量子点的发射波长一般在500～700nm，限制了其在700nm以上波长和500nm以下波长范围的应用。而且现有技术合成的磷化铟纳米晶的光学性能，如发光效率、荧光发射峰半峰宽等，相对于II-VI族元素纳米晶都还存在非常明显的差距。
优化磷化铟纳米晶的制备方法，扩大波长范围，提升量子产率，减小半峰宽具有非常重要的意义。
发明内容
针对上述技术问题，本申请提供一种磷化铟纳米晶的制备方法。
根据本申请的一个方面，提供一种磷化铟纳米晶的制备方法，包括步骤，采用M-(O-C≡P)n作为反应前驱体之一，其中，M为金属元素，n为M元素的化合价价态值；比如，n为1、2或者3。
进一步地，M-(O-C≡P)n为Li-O-C≡P、Na-O-C≡P、K-O-C≡P、Zn-(O-C≡P) 2或者Ga-(O-C≡P) 3。进一步地，磷化铟纳米晶含有M、In和P元素，以及可选的Zn元素。进一步地，反应前驱体还包括铟前驱体。进一步地，反应前驱体还包括锌前驱体。进一步地，包括步骤：对包含有铟前驱体、M-(O-C≡P)n、可选的锌前驱体、和溶剂的溶液进行高温处理，得到磷化铟纳米晶核，高温反应的温度为150℃至340℃之间，优选为150～300℃之间。进一步地，包括步骤：在纳米晶核上包覆壳层。进一步地，溶剂为配位化合物。进一步地，配位化合物为胺或者羧酸。
根据本申请的另一个方面，提供一种磷化铟纳米晶，由上述制备方法制得。
有益效果：本申请采用M-(O-C≡P) n作为反应前驱体之一，由于金属元素M与P元素来自同一反应前驱体，能制备含有In、P和金属元素M的纳米晶核的纳米晶，所制备得到的磷化铟纳米晶的发光波长范围广，发光性能优良。
本申请还提供一种近红外磷化铟纳米晶的制备方法。
根据本申请的一个方面，提供一种近红外磷化铟纳米晶的制备方法，包括步骤：S1、获得包含铟前驱体的第一溶液体系、包含磷前驱体的第二溶液体系；S2、在预定温度下，使包含铟前驱体的第一溶液体系与包含磷前驱体的第二溶液体系混合并反应，得到磷化铟纳米晶；其中，包含铟前驱体的第一溶液体系包括铟前驱体和分散铟前驱体的第一有机溶剂，包含磷前驱体的第二溶液体系包括磷前驱体和分散磷前驱体的第二有机溶剂，第一有机溶剂与第二有机溶剂不相同，第二有机溶剂的沸点低于的预定温度。
进一步的，第二有机溶剂的沸点比的预定温度低至少30℃；优选地，合成方法还包括步骤S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质，在近红外磷化铟纳米晶表面形成壳体，以使近红外磷化铟纳米晶的荧光发射峰峰值在700～900nm。
进一步地，预定温度的范围为180～320℃，第二有机溶剂的沸点在60～150℃。进一步地，磷前驱体的化学结构式为M—(O—C≡P) n，其中，M为金属元素，n为1、2或者3。进一步地，第二有机溶剂包括苯、甲苯、环己烷、正己烷、正庚烷、正辛烷、四氢呋喃、氯仿中的至少一种。进一步地，铟前驱体为卤化铟。进一步地，第一有机溶剂为碳原子数≥6的饱和或者不饱和胺中的至少一种。进一步地，包含铟前驱体的第一溶液体系中还包括锌前驱体。进一步地，在磷化铟纳米晶上包覆壳层。
根据本申请的另一个方面，提供一种近红外磷化铟纳米晶，由上述制备方法制得。进一步地，近红外磷化铟纳米晶的发射峰峰值在700～900nm。
有益效果：通过本申请的制备方法，使用新型磷前驱体，在预定温度下，使含有铟前驱体的第一溶液体系与含有磷前驱体的第二溶液体系混合反应，并且第二有机溶剂的沸点低于预定温度，从而能够一步直接获得波长范围在700～900nm的磷化铟纳米晶，实现了磷化铟纳米晶在近红外波长范围的应用，从而拓宽了磷化铟纳米晶的应用范围。
本申请提供一种光学性能好的红光磷化铟纳米晶的制备方法。
根据本申请的一个方面，提供一种红光磷化铟纳米晶的制备方法，包括步骤：S1、使铟前驱体、磷前驱体与有机溶剂混合，于第一温度下反应，并保温一段时间，得到磷化铟纳米晶核溶液；S2、将磷化铟纳米晶核溶液迅速升温至第二温度，保温一段时间；S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质，得到红光磷化铟纳米晶，红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。
进一步地，第一温度的范围在110～160℃。进一步地，第二温度的范围在280～340℃。进一步地，S2中，将磷化铟纳米晶核溶液迅速升温至第二温度，保持至少10min。进一步地，有机溶剂选自碳原子数≥6的饱和或者不饱和胺中的至少一种。进一步地，磷前驱体的化学结构式为M—(O—C≡P) n，其中，M为金属元素，n为1、2或者3。进一步地，磷化铟纳米晶核溶液中含有第一锌前驱体。进一步地，第一锌前驱体选自卤化锌。进一步地，以物质的量计，第一锌前驱体与铟前驱体的比值为(0.01～10):1。进一步地，纳米晶的壳包括ZnS、ZnSe、ZnSeS中的至少一种。
根据本申请的另一个方面，提供一种红光磷化铟纳米晶，由上述制备方法制得。
进一步地，红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。
借由上述方案，本申请的有益效果在于：
本申请采用“低温成核-快速升温助核生长-最后包壳”的制备方法，得到了荧光发射峰峰值在580～670nm的红光磷化铟纳米晶，其荧光发射峰半峰宽小(≤50nm)、荧光量子产率高(＞80％)，满足磷化铟纳米晶的应用使用需求。
本申请提供一种荧光量子产率高的青光磷化铟纳米晶的制备方法。
根据本申请的一个方面，提供一种青光磷化铟纳米晶的制备方法，包括步骤：S1、使铟前驱体、磷前驱体与有机溶剂混合，于第一温度下反应，得到磷化铟纳米晶核溶液；S2、第一温度下，于磷化铟纳米晶核溶液中加入锌的阳离子前体，形成第一混合液；S3、第二温度下，于第一混合液中加入硫或硒阴离子前体，阳离子前体与阴离子前体反应为磷化铟纳米晶核包覆壳层，得到青光磷化铟纳米晶，青光磷化铟纳米晶的荧光发射峰峰值在460～500nm；其中，第二温度大于第一温度。
进一步地，第一温度的范围在110～160℃。进一步地，第二温度的范围在160～240℃，优选为160～200℃。进一步地，有机溶剂选自碳原子数≥6的饱和或者不饱和胺中的至少一种。进一步地，磷前驱体的化学结构式为M—(O—C≡P) n，其中，M为金属元素，n为1、2或者3。进一步地，磷化铟纳米晶核溶液中含有第一锌前驱体。进一步地，第一锌前驱体选自卤化锌。进一步地，以物质的量计，步骤S2中的阳离子前体与步骤S1中的铟前驱体的比值为(8～40):1。进一步地，阳离子前体为第二锌前驱体；，第二锌前驱体选自羧酸锌或有机锌。进一步地，阴离子前体为硫前体、硒前体中的至少一种。
根据本申请的另一个方面，提供一种青光磷化铟纳米晶，由上述制备方法制得。
进一步地，青光磷化铟纳米晶的荧光发射峰峰值在460～500nm。
借由上述方案，本申请的有益效果在于：
通过本申请的制备方法，能够获得波长范围在460～500nm的青光磷化铟纳米晶。该磷化铟纳米晶的荧光量子产率高(＞50％)，从而拓宽了磷化铟纳米晶的应用使用范围。
本申请的制备方法操作简便、效率高，满足规模化生产的需要，对于实现高质量磷化铟纳米晶材料在下一代显示方面的实际应用具有较高的价值。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为本申请一个示意性的实施例中纳米晶的结构示意图；
图2为实施例15中纳米晶的透射电子显微镜图；
图3为实施例15中纳米晶的荧光发射光谱图。
具体实施方式
下面将结合本申请实施方式，对本申请实施例中的技术方案进行详细的描述。应注意的是，所描述的实施方式仅仅是本申请一部分实施方式，而不是全部实施方式。
需说明的是，下文中的铟前驱体、铟前驱体、铟前驱体均为同一概念，磷源、磷前体、磷前驱体均为同一概念，锌源、锌前体、锌前驱体均为同一概念，硫源、硫前体、硫前体均为同一概念。
图1是本申请一个示意性的实施例中所制备得到的磷化铟纳米晶的结构示意图，纳米晶100包括纳米晶核101，纳米晶核101包括In、P、金属元素M和可选的Zn；以及设置在纳米晶核101上的壳102。
本申请示意性的实施方式，磷化铟纳米晶的制备方法中，包括步骤：采用M-(O-C≡P) n作为反应前驱体之一，其中，M为金属元素，n为M的化合价价态，比如n为1、2或者3。
当M元素为一价的金属元素如Li、Na、K、Rb、Cs等时，n为1。当M元素为二价的金属元素如Zn、Ca、Mn、Sr等时，n为2。当M元素为三价的金属元素如Al、Ga、Tl等时，n为3。优选地，M-(O-C≡P) n为Li-O-C≡P、Na-O-C≡P、K-O-C≡P、Zn-(O-C≡P) 2或者Ga-(O-C≡P) 3。
采用M-(O-C≡P) n作为反应前驱体时，可以得到含有P元素和M元素的合金磷化铟纳米核，从而改善磷化铟纳米晶的发光性能。且由于M元素与P元素来自于同一反应前驱体，可以避免现有技术中，M元素与P元素来自不同前驱体时，配比不易控制的问题。
M-(O-C≡P) n可以根据现有技术中的方法合成。
上述反应前驱体中还包括铟前驱体，铟前驱体优选为铟的卤化物，比如，氯化铟、溴化铟、碘化铟。反应前驱体中还可以包括锌前驱体，锌前驱体优选包括羧酸锌。磷化铟纳米晶的制备包括首先制备磷化铟纳米晶核，接着在磷化铟纳米晶核的表面包括壳层。磷化铟纳米晶核的制备包括步骤：对包含有铟前驱体、M-(O-C≡P) n和溶剂的溶液进行高温处理，其中高温处理的温度优先在150℃至300℃之间，更优选在180℃至240℃之间。溶剂优先为配位化合物，配位化合物包括羧酸，如油酸、豆蔻酸等；配位化合物也可以为胺，如油胺、十八胺、十四胺等。
应理解，本发明的制备方法如无特殊说明，均与现有技术中制备纳米晶时所需要的反应环境相同。在反应之前，使用惰性气体气氛或已经除去湿气和氧气的空气气氛去除反应容器中的湿气和氧气，并使实验中的各个反应过程都在惰性气体气氛的保护下进行。其中，惰性气体气氛包括氮气、氩气或者稀有气体中的至少一种。应理解，由于溶剂在不同压力下的沸点不同，本申请中溶剂的沸点均指标准大气压下的沸点。
本申请提供了一种近红外磷化铟纳米晶的制备方法，包括步骤：S1、获得包含铟前驱体及可选的锌前驱体的第一溶液体系、包含M-(O-C≡P) n作为磷前驱体的第二溶液体系；其中，M为金属元素，n为1、2或者3；S2、在预定温度下，使包含铟前驱体的第一溶液体系与包含磷前驱体的第二溶液体系混合并反应，得到磷化铟纳米晶；其中，包含铟前驱体的第一溶液体系包括铟前驱体和分散铟前驱体的第一有机溶剂，包含磷前驱体的第二溶液体系包括磷前驱体和分散磷前驱体的第二有机溶剂，第一有机溶剂与第二有机溶剂不相同，第二有机溶剂的沸点低于所述的预定温度。
在本申请的一个优选实施方式中，所述第二有机溶剂的沸点比所述的预定温度低至少30℃。优选地，上述合成方法还包括步骤S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质，在所述近红外磷化铟纳米晶表面形成壳体，以使所述近红外磷化铟纳米晶的荧光发射峰峰值在700nm～900nm。
根据本申请的一种优选实施方式，本申请S2中使包含铟前驱体的第一溶液体系与包含磷前驱体的第二溶液体系混合并反应的温度范围为180～320℃，所述第二有机溶剂的沸点小于等于150℃，优选在60～150℃。
在一个具体的实施方式中，首先将包含铟前驱体的第一溶液体系的温度调节至180～280℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；接着，将铟-磷混合溶液体系升温至280～320℃，保温并反应一段时间，得到包含磷化铟纳米晶的溶液体系。
进一步地，当M元素为一价的金属元素如Li、Na、K、Rb、Cs等时，n为1。当M元素为二价的金属元素如Zn、Ca、Mn、Sr等时，n为2。当M元素为三价的金属元素如Al、Ga、Tl等时，n为3。在一些具体的实施方式中，磷前驱体M—(O—C≡P) n为Li—O—C≡P、Na—O—C≡P、K—O—C≡P、Zn—(O—C≡P) 2或者Ga—(O—C≡P) 3。
本申请中，选择M—(O—C≡P) n作为合成磷化铟纳米晶的新磷前驱体。使铟前驱体和M—(O—C≡P)n混合并在预定温度下反应，可以仅通过一次加料的方式获得波长范围在700～900nm的磷化铟纳米晶。同时，本申请的磷前驱体M—(O—C≡P) n还可以提供金属元素M，从而制备出具有由In、P和金属元素M构成的合金核的纳米晶，进一步优化磷化铟纳米晶的光学性能。
根据本申请的一种优选实施方式，第二有机溶剂包括苯、甲苯、环己烷、正己烷、正庚烷、正辛烷、四氢呋喃、氯仿中的至少一种。
根据本申请的一种优选实施方式，铟前驱体为卤化铟。在一些具体的实施方式中，铟前驱体包括氯化铟、溴化铟、碘化铟中的至少一种。
根据本申请的一种优选实施方式，第一有机溶剂为碳原子数≥6的饱和或者不饱和胺中的至少一种。在一个具体的实施方式中，第一有机溶剂包括己胺、庚胺、辛胺、三辛胺、壬胺、十胺、十烯胺、十一胺、十一烯胺、十二胺、十二烯胺、十三胺、十三烯胺、十四胺、十五胺、十五烯胺、十六胺、十七胺、十八胺、十八烯胺、油胺、十烯胺、十一烯胺、十二烯胺、十三烯胺、十四烯胺、十五烯胺、十六烯胺、十七烯胺、十八烯胺中的至少一种。
根据本申请的一种优选实施方式，包含铟前驱体的第一溶液体系中还包括锌前驱体。在一些具体的实施方式中，锌前驱体包括醋酸锌、氯化锌、碳酸锌、十酸锌、十一烯酸锌、硬脂酸锌、油酸锌和二乙基二硫氨基甲酸锌中的至少一种。
发明人发现，在制备磷化铟纳米晶的过程中，将一定量的锌前驱体引入到反应体系中，可以进一步降低纳米晶核的表面缺陷，增强纳米晶的能级发光效率。
根据本申请的一种优选实施方式，在磷化铟纳米晶上包覆壳层。在一个具体的实施方式中，向包含纳米晶的溶液体系中加入合成壳层所需前体物质，得到包覆壳层的磷化铟纳米晶。其中，合成壳层所需前体物质包括锌前驱体，以及硫前驱体和硒前驱体中的至少一种。
根据本申请的一种优选实施方式，为了进一步提高所制备的磷化铟纳米晶的光学性能，在得到上述磷化铟纳米晶后，还包括除去未反应的原料及其他杂质的步骤，具体包括分离和提纯。这些步骤是本领域的公知方法，这里不再赘述。
根据本申请的一种优选实施方式，提供一种磷化铟纳米晶，由上述制备方法制得，磷化铟纳米晶的发射峰峰值在700nm以上，优选在700～900nm。
现有技术中，为了获得大波长的磷化铟纳米晶，常常会采用增大磷化铟纳米晶尺寸的方法。但这种方法常常会带来表面缺陷增大、波长调控难等问题，并不能满足应用要求。本申请制备方法可以仅通过一步法直接获得发射波长在700～900nm的磷化铟纳米晶。
根据本申请的一种优选实施方式，磷化铟纳米晶含有M、In和P元素，其中M为金属元素。发明人发现，与单纯的由In、P两种元素构成的磷化铟纳米晶相比，本申请含有M、In和P元素构成的磷化铟纳米晶的表面缺陷较少，且磷化铟纳米晶的发光中心不含有重金属元素，更加环保，应用范围广。
在一个具体的实施方式中，磷化铟纳米晶的构成元素还包括Zn，但本发明磷化铟纳米晶的构成元素并不限于此。
根据本申请的一种优选实施方式，磷化铟纳米晶外包覆有壳层，其中，壳层含有Zn元素，以及S元素和Se元素中的至少一种。在一个具体的实施方式中，壳层为ZnS、ZnSe和ZnSeS中的至少一种。
发明人发现，将ZnS和/或ZnSe和/或ZnSeS壳层生长在磷化铟纳米晶的表面，有利于获得具有更好稳定性和更优良光学性质的磷化铟纳米晶。
本申请提供了一种红光磷化铟纳米晶的制备方法，包括步骤：S1、使铟前驱体、磷前驱体与有机溶剂混合，于第一温度下反应并保温一段时间，得到磷化铟纳米晶核溶液；S2、将磷化铟纳米晶核溶液迅速升温至第二温度，并保温一段时间；S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质，得到红光磷化铟纳米晶，该红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。
根据本申请的一种优选实施方式，第一温度的范围在110～160℃，优选第二温度的范围在280～340℃。
根据本申请的一种优选实施方式，S2中，将磷化铟纳米晶核溶液迅速升温至第二温度，保持至少10min。
根据本申请的一种优选实施方式，将磷化铟纳米晶核溶液迅速升温至第二温度所需要的时间控制在10min以内。发明人发现，在上述“迅速升温”的时间范围内将反应体系的温度从第一温度调至第二温度，有利于磷化铟纳米晶核快速聚集和生长，从而获得粒径均匀的纳米晶。
现有技术被广泛采用的磷化铟纳米晶的制备方法通常为高温注入法，使铟前驱体与磷前驱体直接在高温下快速成核并生长成熟，然后按需包覆壳层，可以制备出波长范围在520-720nm的纳米晶。但是，高温注入法很难平衡纳米晶的成核和生长过程，使得所制备的纳米晶的尺寸分布不均匀、半峰宽变宽。
在本申请中，使铟前驱体、磷前驱体与有机溶剂混合并反应的温度为120～160℃。发明人发现，在该较低的第一温度下制备磷化铟纳米晶核，可以控制纳米晶核的成核和生长过程，使合成的纳米晶的尺寸分布变得均匀，半峰宽变窄。此外，该较低的第一温度还可以有效避免磷化铟纳米晶核表面被氧化的风险，从而更利于自由的单体反应物在晶种表面上的生长过程，使制备的磷化铟纳米晶具有更好的光学性能。
在本申请中，将上述磷化铟纳米晶核溶液迅速升温至280～320℃，保持一段至少10min。发明人发现，在该较高的第二温度下，磷化铟纳米晶核进一步聚集、生长，体系中磷化铟纳米晶核的粒径逐渐变大，从而实现了磷化铟纳米晶核的“熟化过程”。接着，将合成壳所需的前体物质加入到上述含有磷化铟纳米晶核的混合体系中，实现纳米晶的壳层包覆过程，并最终获得了具有壳层包覆的红光磷化铟纳米晶。
本申请采用“低温成核-快速升温助核生长-最后包壳”的技术手段，首先在较低的第一温度下制备磷化铟纳米晶核，接着通过迅速升温的方式控制纳米晶核的进一步聚集和生长，最后在纳米晶核表面形成纳米晶的壳，由此，通过控制反应温度，有效地平衡了磷化铟纳米晶的成核、生长和包覆过程，得到了具有核壳结构的、荧光发射峰峰值在580-670nm的红光磷化铟纳米晶。
根据本申请的一种优选实施方式，有机溶剂选自碳原子数≥6的饱和或者不饱和胺中的至少一种。
根据本申请的一种优选实施方式，有机溶剂选自一级胺、二级胺中的至少一种。在一个具体的实施方式中，有机溶剂选自己胺、庚胺、辛胺、壬胺、十胺、十烯胺、十一胺、十一烯胺、十二胺、十二烯胺、十三胺、十三烯胺、十四胺、十四烯胺、十五胺、十五烯胺、十六胺、十六烯胺、十七胺、十七烯胺、十八胺和十八烯胺中的至少一种。
根据本申请的一种优选实施方式，磷前驱体的化学结构式为M—(O—C≡P) n，其中，M为金属元素，n为1、2或者3。进一步地，当M元素为一价的金属元素如Li、Na、K、Rb、Cs等时，n为1。当M元素为二价的金属元素如Zn、Ca、Mn、Sr等时，n为2。当M元素为三价的金属元素如Al、Ga、Tl等时，n为3。
在本申请中，发明人发现，磷前驱体M—(O—C≡P) n可以提供金属元素M，制备出具有由In、P和金属元素M构成的合金核的纳米晶，从而进一步优化磷化铟纳米晶的光学性能。在一个具体的实施方式中，磷前驱体M—(O—C≡P) n为Li—O—C≡P、Na—O—C≡P、K—O—C≡P、Zn—(O—C≡P) 2或者Ga—(O—C≡P) 3。
根据本申请的一种优选实施方式，磷化铟纳米晶核溶液中含有第一锌前驱体。根据本申请的一种优选实施方式，第一锌前驱体选自卤化锌。在一个具体的实施方式中，第一锌前驱体选自氯化锌、溴化锌、碘化锌中的至少一种。
发明人发现，在制备磷化铟纳米晶核的过程中，将一定量的锌前驱体引入到反应体系中，可以进一步降低纳米晶核的表面缺陷，增强磷化铟纳米晶的能级发光效率。
根据本申请的一种优选实施方式，以物质的量计，第一锌前驱体与铟前驱体的比值为(0.01～10):1。在一个具体的实施方式中，以物质的量计，第一锌前驱体与铟前驱体的比值为(0.1～1):1。
根据本申请的一种优选实施方式，纳米晶的壳包括ZnS、ZnSe、ZnSeS中的至少一种。
在本申请中，发明人发现，使纳米晶的壳生长在纳米晶核表面，可以显著提高纳米晶的发光效率和光化学稳定性。根据本申请的一种优选实施方式，纳米晶的壳包括至少两层壳，其中，至少两层壳邻近且彼此不同。在一个具体的实施方式中，纳米晶的壳包括两层壳，其中，远离磷化铟纳米晶核的壳为ZnS，靠近磷化铟纳米晶核的壳为ZnSe，或者ZnSeS。
根据本发明的一种优选实施方式，合成纳米晶的壳所需的前体物质包括第二锌前驱体，以及硫前体、硒前体中的至少一种。在一个具体的实施方式中，第二锌前驱体选自羧酸锌，或者有机锌试剂(锌与烷基直接相连的试剂)。优选地，第二锌前驱体选自醋酸锌、硬脂酸锌、油酸锌、十酸锌、十一烯酸锌、十四酸锌、十六酸锌、二乙基二硫氨基甲酸锌中、二乙基锌的至少一种。在一个具体的实施方式中，硫前体选自烷基硫醇、单质硫溶解在溶剂中所形成的溶液中的至少一种。优选地，硫前体选自烷基硫醇、硫化三烷基膦、硫化三烯基膦、硫的有机胺溶液中的至少一种。进一步优选地，硫前体选自硫化三正丁基膦、硫化三辛基膦、硫的油胺溶液中的至少一种。在一个具体的实施方式中，硒前体选自单质硒溶解在溶剂中所形成的溶液。优选地，硒前体选自硒化三烷基膦、硒化三烯基膦、硒的有机胺溶液中的至少一种。进一步优选地，硒前体选自硒化三正丁基膦、硒化三辛基膦、硒的油胺溶液中的至少一种。
在本申请中，发明人发现，上述锌前驱体、硫前体、硒前体的反应活性较高，有利于为磷化铟纳米晶核包覆质量高的壳层。以上述锌前驱体、硫前体、硒前体作为合成纳米晶的壳所需的前体物质，可以使得纳米晶的壳层的生长更加均匀，从而有效提高磷化铟纳米晶的荧光量子产率。
根据本申请的一种优选实施方式，红光磷化铟纳米晶的制备方法还包括步骤：S4、继续升温，于S3的反应体系中再次加入合成纳米晶的壳所需的前体物质，得到红光磷化铟纳米晶，该红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。在本申请中，发明人发现，根据实际需要，多次和重复为磷化铟纳米晶核包覆壳层，可以使壳层更好、更均匀地覆盖在磷化铟纳米晶核的表面，从而进一步提高磷化铟纳米晶的发光效率和光化学稳定性。
根据本申请的一种优选实施方式，为了进一步提高所制备的磷化铟纳米晶的光学性能，在得到上述磷化铟纳米晶后，还包括除去未反应的原料及其他杂质的步骤，具体包括分离和提纯。这些步骤是本领域的公知方法，这里不再赘述。
根据本申请的一种优选实施方式，提供一种红光磷化铟纳米晶，该红光磷化铟纳米晶由以下步骤制得：S1、使铟前驱体、磷前驱体与有机溶剂混合，于第一温度下反应，得到磷化铟纳米晶核溶液；S2、将磷化铟纳米晶核溶液迅速升温至第二温度，保持一段时间；S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质，得到红光磷化铟纳米晶，该红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。
根据本申请的一种优选实施方式，第一温度的范围在110～160℃。优选第二温度的范围在280～340℃。
根据本申请的一种优选实施方式，S2中，将磷化铟纳米晶核溶液迅速升温至第二温度，保持至少10min。
根据本申请的一种优选实施方式，有机溶剂选自碳原子数≥6的饱和或者不饱和胺中的至少一种。根据本申请的一种优选实施方式，有机溶剂选自一级胺、二级胺中的至少一种。在一个具体的实施方式中，有机溶剂选自己胺、庚胺、辛胺、壬胺、十胺、十烯胺、十一胺、十一烯胺、十二胺、十二烯胺、十三胺、十三烯胺、十四胺、十四烯胺、十五胺、十五烯胺、十六胺、十六烯胺、十七胺、十七烯胺、十八胺和十八烯胺中的至少一种。
根据本申请的一种优选实施方式，磷前驱体的化学结构式为M—(O—C≡P) n，其中，M为金属元素，n为1、2或者3。进一步地，当M元素为一价的金属元素如Li、Na、K、Rb、Cs等时，n为1。当M元素为二价的金属元素如Zn、Ca、Mn、Sr等时，n为2。当M元素为三价的金属元素如Al、Ga、Tl等时，n为3。在一个具体的实施方式中，磷前驱体M—(O—C≡P) n为Li—O—C≡P、Na—O—C≡P、K—O—C≡P、Zn—(O—C≡P) 2或者Ga—(O—C≡P) 3。
根据本申请的一种优选实施方式，磷化铟纳米晶核溶液中含有第一锌前驱体。根据本申请的一种优选实施方式，第一锌前驱体选自卤化锌。在一个具体的实施方式中，第一锌前驱体选自氯化锌、溴化锌、碘化锌中的至少一种。
根据本申请的一种优选实施方式，以物质的量计，第一锌前驱体与铟前驱体的比值为(0.01～10):1。在一个具体的实施方式中，以物质的量计，第一锌前驱体与铟前驱体的比值为(0.1～1):1。
根据本申请的一种优选实施方式，纳米晶的壳包括ZnS、ZnSe、ZnSeS中的至少一种。
根据本申请的一种优选实施方式，纳米晶的壳包括至少两层壳，其中，至少两层壳邻近且彼此不同。
在一个具体的实施方式中，纳米晶的壳包括两层壳，其中，远离磷化铟纳米晶核的壳为ZnS，靠近磷化铟纳米晶核的壳为ZnSe，或者ZnSeS。
根据本申请的一种优选实施方式，该红光磷化铟纳米晶还可以由以下步骤制得：S1、使铟前驱体、磷前驱体与有机溶剂混合，于第一温度下反应，得到磷化铟纳米晶核溶液；S2、将所述磷化铟纳米晶核溶液迅速升温至第二温度，保持一段时间；S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质；S4、继续升温，于S3的反应体系中再次加入合成纳米晶的壳所需的前体物质，得到红光磷化铟纳米晶，该红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。
在本申请中，发明人发现，该磷化铟纳米晶的发光性能优良，荧光发射峰半峰宽小(≤50nm)、荧光量子产率高(＞80％)。现有技术中合成的红光磷化铟往往半峰宽大，量子产率低且稳定性不佳。通过新型磷前驱体的使用，在核中掺杂了M元素，提高了量子产率；两步温度的调控，减小了半峰宽，使得合成的产品拥有更好的性能。
本申请提供了一种青光磷化铟纳米晶的制备方法，包括步骤：S1、使铟前驱体、可选的锌前驱体、磷前驱体M-(O-C≡P) n与有机溶剂混合，于第一温度下反应，得到磷化铟纳米晶核溶液；S2、第一温度下，于磷化铟纳米晶核溶液中加入锌的阳离子前体，形成第一混合液；S3、第二温度下，于第一混合液中加入硫或硒阴离子前体，阳离子前体与阴离子前体反应为磷化铟纳米晶核包覆壳层，得到青光磷化铟纳米晶，该青光磷化铟纳米晶的荧光发射峰峰值在460～500nm；其中，第二温度大于第一温度。
在一个具体的实施方式中，首先将包含铟前驱体和磷前驱体的溶液体系升温至110-160℃，保温一段时间后加入锌的阳离子前体，其中所述锌的阳离子前体与步骤S1中所述的铟前驱体的比值为(8～40):1。接着升温到第二反应温度160-240℃，加入与锌等摩尔量的硫或硒阴离子前体，得到包含磷化铟纳米晶的溶液体系。
根据本申请的一种优选实施方式，第一温度的范围在110～160℃。优选第二温度的范围在160～200℃。
根据本申请的一种优选实施方式，有机溶剂选自碳原子数≥6的饱和或者不饱和胺、或者羧酸中的至少一种。在一个具体的实施方式中，有机溶剂选自己胺、庚胺、辛胺、壬胺、十胺、十烯胺、十一胺、十一烯胺、十二胺、十二烯胺、十三胺、十三烯胺、十四胺、十四烯胺、十五胺、十五烯胺、十六胺、十六烯胺、十七胺、十七烯胺、十八胺和十八烯胺中的至少一种。
根据本申请的一种优选实施方式，磷前驱体的化学结构式为M—(O—C≡P) n，其中，M为金属元素，n为M元素的化合价价态，比如n为1、2或者3。在一个具体的实施方式中，磷前驱体M—(O—C≡P) n为Li—O—C≡P、Na—O—C≡P、K—O—C≡P、Zn—(O—C≡P) 2或者Ga—(O—C≡P) 3。
在本申请中，选择M—(O—C≡P) n作为合成磷化铟纳米晶的新磷前驱体。使铟前驱体和M—(O—C≡P)n混合并升温到第一温度反应得到最终的磷化铟纳米晶溶液，然后迅速进行壳层的包覆。同时，本申请的磷前驱体M—(O—C≡P) n还可以提供金属元素M，从而制备出具有由In、P和金属元素M构成的合金核的纳米晶，进一步优化磷化铟纳米晶的光学性能。
根据本申请的一种优选实施方式，磷化铟纳米晶核溶液中可选的含有第一锌前驱体，第一锌前驱体选自卤化锌。在一个具体的实施方式中，第一锌前驱体选自氯化锌、溴化锌、碘化锌中的至少一种。在一个具体的实施方式中，锌源包括醋酸锌、氯化锌、碳酸锌、十酸锌、十一烯酸锌、硬脂酸锌、油酸锌和二乙基二硫氨基甲酸锌中的至少一种。发明人发现，在制备磷化铟纳米晶核的过程中，将一定量的锌前驱体引入到反应体系中，可以进一步降低纳米晶核的表面缺陷，增强纳米晶的能级发光效率。
根据本申请的一种优选实施方式，以物质的量计，第一锌前驱体与铟前驱体的比值为(3～20):1。在一个具体的实施方式中，以物质的量计，第一锌前驱体与铟前驱体的比值为(3～10):1。
根据本申请的一种优选实施方式，以物质的量计，步骤S2中的锌的阳离子前体与步骤S1中的铟前驱体的比值为(8～40):1。在一个具体的实施方式中，以物质的量计，步骤S2中锌的阳离子前体与步骤S1中的铟前驱体的比值为(10～20):1。
根据本申请的一种优选实施方式，阳离子前体为第二锌前驱体。根据本申请的一种优选实施方式，第二锌前驱体选自有机锌试剂。在一个具体的实施方式中，第二锌前驱体选自醋酸锌、硬脂酸锌、油酸锌、十酸锌、十一烯酸锌、十四酸锌、十六酸锌、二乙基锌中的至少一种。根据本申请的一种优选实施方式，阴离子前体为硫前体、硒前体中的至少一种。根据本申请的一种优选实施方式，硫前体选自烷基硫醇、单质硫溶解在溶剂中所形成的溶液中的至少一种。在本申请的一个具体实施例中，硫前体选自烷基硫醇、硫化三烷基膦、硫化三烯基膦、硫的有机胺溶液中的至少一种。优选地，硫前体选自硫化三正丁基膦、硫化三辛基膦、硫的油胺溶液中的至少一种。根据本申请的一种优选实施方式，硒前体选自单质硒溶解在溶剂中所形成的溶液。在本申请的一个具体实施例中，硒前体选自硒化三烷基膦、硒化三烯基膦、硒的有机胺溶液中的至少一种。优选地，硒前体选自硒化三正丁基膦、硒化三辛基膦、硒的油胺溶液中的至少一种。
在本申请中，发明人发现，上述硫前体、硒前体的反应活性较高，有利于为磷化铟纳米晶核包覆质量高的壳层。以上述硫前体、硒前体作为阴离子前体，可以使得纳米晶的壳层的生长更加均匀，从而有效提高磷化铟纳米晶的荧光量子产率。
根据本申请的一种优选实施方式，青光磷化铟纳米晶的制备方法还包括步骤：S4、于步骤S3的反应体系中再次加入阳离子前体和阴离子前体，得到青光磷化铟纳米晶，该青光磷化铟纳米晶的荧光发射峰峰值在460～500nm。在本申请中，发明人发现，根据实际需要，多次和重复为磷化铟纳米晶核包覆壳层，可以使壳层更好、更均匀地覆盖在磷化铟纳米晶核的表面，从而进一步提 高磷化铟纳米晶的发光效率和光化学稳定性。根据本申请的一种优选实施方式，S4是在逐渐提高反应体系的温度下进行的。
根据本申请的一种优选实施方式，为了进一步提高所制备的磷化铟纳米晶的光学性能，在得到上述磷化铟纳米晶后，还包括除去未反应的原料及其他杂质的步骤，具体包括分离和提纯。这些步骤是本领域的公知方法，这里不再赘述。
根据本申请的一种优选实施方式，提供一种青光磷化铟纳米晶，该青光磷化铟纳米晶由以下步骤制得：S1、使铟前驱体、磷前驱体与有机溶剂混合，于第一温度下反应，得到磷化铟纳米晶核溶液；S2、第一温度下，于磷化铟纳米晶核溶液中加入阳离子前体，形成第一混合液；S3、第二温度下，于第一混合液中加入阴离子前体，阳离子前体与阴离子前体反应为磷化铟纳米晶核包覆壳层，得到青光磷化铟纳米晶，该青光磷化铟纳米晶的荧光发射峰峰值在460～500nm；其中，第二温度大于第一温度。
根据本申请的一种优选实施方式，第一温度的范围在110～160℃。优选第二温度的范围在160～200℃。
根据本申请的一种优选实施方式，有机溶剂选自碳原子数≥6的饱和或者不饱和胺中的至少一种。在一个具体的实施方式中，有机溶剂选自己胺、庚胺、辛胺、壬胺、十胺、十烯胺、十一胺、十一烯胺、十二胺、十二烯胺、十三胺、十三烯胺、十四胺、十四烯胺、十五胺、十五烯胺、十六胺、十六烯胺、十七胺、十七烯胺、十八胺和十八烯胺中的至少一种。
根据本申请的一种优选实施方式，磷前驱体的化学结构式为M—(O—C≡P) n，其中，M为金属元素，n为M元素的化合价价态，比如n为1、2或者3。进一步地，当M元素为一价的金属元素如Li、Na、K、Rb、Cs等时，n为1。当M元素为二价的金属元素如Zn、Ca、Mn、Sr等时，n为2。当M元素为三价的金属元素如Al、Ga、Tl等时，n为3。在一个具体的实施方式中，磷前驱体M—(O—C≡P) n为Li—O—C≡P、Na—O—C≡P、K—O—C≡P、Zn—(O—C≡P) 2或者Ga—(O—C≡P) 3。
根据本申请的一种优选实施方式，磷化铟纳米晶核溶液中含有第一锌前驱体。根据本申请的一种优选实施方式，第一锌前驱体选自卤化锌。在一个具体的实施方式中，第一锌前驱体选自氯化锌、溴化锌、碘化锌中的至少一种。
根据本申请的一种优选实施方式，以物质的量计，第一锌前驱体与铟前驱体的比值为(3～20):1。在一个具体的实施方式中，以物质的量计，第一锌前驱体与铟前驱体的比值为(3～10):1。根据本申请的一种优选实施方式，以物质的量计，步骤S2中的阳离子前体与步骤S1中的铟前驱体的比值为(8～40):1。在一个具体的实施方式中，以物质的量计，步骤S2中的阳离子前体与步骤S1中的铟前驱体的比值为(10～20):1。
根据本申请的一种优选实施方式，阳离子前体为第二锌前驱体。根据本申请的一种优选实施方式，第二锌前驱体选自羧酸锌、或者有机锌试剂。在一个具体的实施方式中，第二锌前驱体选自醋酸锌、硬脂酸锌、油酸锌、十酸锌、十一烯酸锌、十四酸锌、十六酸锌、二乙基锌中的至少一种。
根据本申请的一种优选实施方式，阴离子前体为硫前体、硒前体中的至少一种。根据本申请的一种优选实施方式，硫前体选自烷基硫醇、单质硫溶解在溶剂中所形成的溶液中的至少一种。在本申请的一个具体实施例中，硫前体选自烷基硫醇、硫化三烷基膦、硫化三烯基膦、硫的有机胺溶液中的至少一种。优选地，硫前体选自硫化三正丁基膦、硫化三辛基膦、硫的油胺溶液中的至少一种。根据本申请的一种优选实施方式，硒前体选自单质硒溶解在溶剂中所形成的溶液。在本申请的一个具体实施例中，硒前体选自硒化三烷基膦、硒化三烯基膦、硒的有机胺溶液中的至少一种。优选地，硒前体选自硒化三正丁基膦、硒化三辛基膦、硒的油胺溶液中的至少一种。
根据本申请的一种优选实施方式，该青光磷化铟纳米晶还可以由以下步骤制得：S1、使铟前驱体、磷前驱体与有机溶剂混合，于第一温度下反应，得到磷化铟纳米晶核溶液；S2、第一温度下，于磷化铟纳米晶核溶液中加入阳离子前体，形成第一混合液；S3、第二温度下，于第一混合液中加入阴离子前体，阳离子前体与阴离子前体反应为磷化铟纳米晶核包覆壳层；S4、于步骤S3的反应体系中再次加入阳离子前体和阴离子前体，得到青光磷化铟纳米晶；其中，第二温度大于第一温度。
根据本申请的一种优选实施方式，磷化铟纳米晶的荧光发射峰峰值在460～500nm。
在本申请中，发明人发现，该磷化铟纳米晶的荧光量子产率高(＞50％)，从而拓宽了磷化铟纳米晶的应用使用范围。现有技术中青光磷化铟的合成方法有限，且合成得到的产品性能不佳。通过新型磷前驱体的使用，青光磷化铟的合成变得简单高效。由于M元素的掺杂，本方法合成得到的产盘波长可控，效率高，半峰宽窄。
以下将参考以下实施例更详细地描述根据本申请的一些示例性实施方式的制备方法；然而，本申请的示例性实施方式不限于此。
近红外光磷化铟纳米晶的制备
实施例1
磷化铟纳米晶1由In、P、Na三种元素构成，壳为ZnSe和ZnS构成的双壳层。第二溶剂为甲苯。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的NaOCP与5mL的甲苯混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将包含铟前驱体的第一溶液体系加热至200℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至280℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温到310℃，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶1。
实施例2
磷化铟纳米晶2由In、P、Na、Zn四种元素构成，壳为ZnSe和ZnS构成的双壳层。第二溶剂为甲苯。
磷化铟纳米晶的制备过程如下：
S1、在30℃下，将0.5mmol的氯化铟、2mmol的氯化锌与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的NaOCP与5mL的甲苯混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将包含铟前驱体的第一溶液体系加热至200℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至280℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温到310℃，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶2。
实施例3
磷化铟纳米晶3由In、P、K、Zn四种元素构成，壳为ZnSe和ZnS构成的双壳层。第二溶剂为甲苯。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟、2mmol的氯化锌与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的KOCP与5mL的甲苯混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将第一溶液体系加热至200℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至280℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温到310℃，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶3。
实施例4
磷化铟纳米晶4由In、P、K三种元素构成，壳为ZnSe和ZnS构成的双壳层。第二溶剂为甲苯。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的KOCP与5mL的甲苯混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将包含铟前驱体的第一溶液体系加热至240℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至300℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温到310℃，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶4。
实施例5
磷化铟纳米晶5由In、P、Na三种元素构成，第二溶剂为正庚烷。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的NaOCP与5mL的正庚烷混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将包含铟前驱体的第一溶液体系加热至200℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至280℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温到310℃，加入24mmol的油酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶5。
实施例6
磷化铟纳米晶6由In、P、Na三种元素构成，第二溶剂为甲苯，240℃成核。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的NaOCP与5mL的甲苯混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将包含铟前驱体的第一溶液体系加热至240℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至280℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温到310℃，加入24mmol的油酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶6。
对比例1
磷化铟纳米晶7由In、P、Na三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的NaOCP与5mL的油胺混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将包含铟前驱体的第一溶液体系加热至240℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至300℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温，24mmol的醋酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶7。
对比例2
磷化铟纳米晶8由In、Zn、P三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、将50mg的氯化铟、150mg的氯化锌和3mL的油胺混合，氮气排气状态下在120℃保温1h；
S2、升温至180℃，快速注入三(二乙基氨基)膦，反应60min；
S3、加入0.5mL的硒-三辛基膦溶液(1mmol/mL)，反应60min，得到包覆在磷化铟纳米晶上的ZnSe壳；
S4、加入500mg硬脂酸锌、2mL十八烯，升温至200℃，反应30min，再加入0.5mL硫-三辛基膦溶液(1mmol/mL)，反应30min，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶8。
对比例3
磷化铟纳米晶9由In、P、Na三种元素构成。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟与10mL的油胺混合，得到包含铟前驱体的第一溶液体系；将0.75mmol的NaOCP与5mL的油胺混合，得到包含磷前驱体的第二溶液体系；
S2、氮气排气状态下将包含铟前驱体的第一溶液体系加热至200℃，加入包含磷前驱体的第二溶液体系，得到铟-磷混合溶液体系；
S3、将步骤S2的铟-磷混合溶液体系加热至280℃，反应60min，得到包含磷化铟纳米晶的溶液体系；
S4、升温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶9。
对比例4
磷化铟纳米晶10由In、Zn、P三种元素构成。
磷化铟纳米晶的制备过程如下：
S1、将50mg的氯化铟、150mg的氯化锌和3mL的油胺混合，氮气排气状态下在120℃保温1h；
S2、升温至200℃，快速注入三(二乙基氨基)膦，反应60min；
S3、升温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S5、反应结束，经分离和提纯，得到磷化铟纳米晶10。
此外，进一步测试实施例1至实施例6、对比例1至对比例4的磷化铟纳米晶的荧光性质。测试结果如下表所示。
Figure PCTCN2020085274-appb-000001
根据上表可知，通过本申请的制备方法，在预定温度下，使含有铟前驱体的第一溶液体系与含有磷前驱体的第二溶液体系混合反应，并且第二有机溶剂的沸点低于预定温度，可以仅通过一次加料的方式、一步直接获得波长范围在700～900nm的磷化铟纳米晶，实现了磷化铟纳米晶在近红外波长范围的应用，从而拓宽了磷化铟纳米晶的应用范围。
红光磷化铟纳米晶的制备
实施例7
红光磷化铟纳米晶11的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、0.5mmol ZnCl 2、20mL油胺、1mmol Na—O—C≡P混合，在120℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟升温至300℃，保持30min；
S3、为磷化铟纳米晶核包覆壳层：于S2的反应体系中加入10mmol醋酸锌和10mmol硫的油胺溶液，反应60min，得到红光磷化铟纳米晶11。
实施例8
红光磷化铟纳米晶12的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、0.5mmol ZnCl 2、20mL油胺、1mmol Na—O—C≡P混合，在120℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟内升温至320℃，保持30min；
S3、为磷化铟纳米晶核包覆壳层：于S2的反应体系中加入10mmol醋酸锌和10mmol硫的油胺溶液，反应60min，得到红光磷化铟纳米晶12。
实施例9
红光磷化铟纳米晶13的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、1mmol ZnCl 2、20mL油胺、1mmol Na—O—C≡P混合，在140℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟内升温至340℃，保持30min；
S3、为磷化铟纳米晶核包覆壳层：于S2的反应体系中加入10mmol醋酸锌和10mmol硫的油胺溶液，反应60min，得到红光磷化铟纳米晶13。
实施例10
红光磷化铟纳米晶14的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、0.5mmol ZnCl 2、20mL油胺、1mmol Na—O—C≡P混合，在120℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟升温至300℃，保持30min；
S3、升温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到磷化铟纳米晶14。
实施例11
红光磷化铟纳米晶15的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、0.5mmol ZnCl 2、20mL油胺、1mmol Na—O—C≡P混合，在120℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟升温至320℃，保持30min；
S3、降温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到磷化铟纳米晶15。
实施例12
红光磷化铟纳米晶16的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、1mmol ZnCl 2、20mL油胺、1mmol Na—O—C≡P混合，在140℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟升温至340℃，保持30min；
S3、降温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到磷化铟纳米晶16。
实施例13
红光磷化铟纳米晶17的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、1mmol ZnCl 2、20mL油胺、1mmol K—O—C≡P混合，在140℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟升温至340℃，保持30min；
S3、降温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到磷化铟纳米晶17。
实施例14
红光磷化铟纳米晶18的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、20mL油胺、1mmol K—O—C≡P混合，在140℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟升温至340℃，保持30min；
S3、降温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到磷化铟纳米晶18。
对比例5
磷化铟纳米晶19的制备：
S1、获得磷化铟纳米晶核溶液：使1mmol InCl 3、5mmol ZnCl 2、10mL油胺混合并加热反应，抽真空后充入惰性气体，在300℃下，加入4mmol三(二乙基氨基)膦，反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：于S1的磷化铟纳米晶核溶液中加入6mmol硬脂酸锌的十八稀溶液，再加入6mmol硫化三辛基膦溶液，反应60min，得到磷化铟纳米晶19。
对比例6
红光磷化铟纳米晶20的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、1mmol ZnCl 2，20mL油胺、1mmol Na—O—C≡P混合，10分钟升温至340℃，保持30min；
S2、降温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S3、反应结束，经分离和提纯，得到磷化铟纳米晶20。
对比例7
红光磷化铟纳米晶21的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、1mmol ZnCl 2，20mL油胺、4mmol三(二乙基氨基)膦混合，在140℃下反应30min，得到磷化铟纳米晶核溶液；
S2、磷化铟纳米晶核的生长：将S1的磷化铟纳米晶核溶液10分钟升温至340℃，保持30min；
S3、降温到310℃，24mmol的油酸锌、6mL的硒-三辛基膦(2mmol/mL)并反应，得到包覆在磷化铟纳米晶上的ZnSe壳；再加入6mL硫-三辛基膦(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到磷化铟纳米晶21。
测试表征：分别将实施例7到实施例14中获得的红光磷化铟纳米晶、对比例5至对比例7获得的磷化铟纳米晶分散在甲苯溶液中，测试其荧光光谱和荧光量子产率。具体测试结果如下表所示。
Figure PCTCN2020085274-appb-000002
根据上表可知，本申请的磷化铟纳米晶较对比例而言，荧光发射峰半峰宽小、荧光量子产率高，从而证明通过本申请制备方法获得的磷化铟纳米晶具有优良的发光性能，从而拓宽了磷化铟纳米晶的应用使用范围。
磷化铟纳米晶的制备
实施例15
磷化铟纳米晶核由In、P、Li三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟、0.75mmol的Li-O-C≡P、10mL的油胺混合，得到第一溶液体系；
S2、氮气排气状态下将第一溶液体系加热至180℃，反应60min，得到包含纳米晶核的溶液体系；
S3、升温，加入24mmol的硬脂酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到纳米晶。
实施例16
磷化铟纳米晶核由In、P、Na三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟、0.75mmol的Na-O-C≡P、10mL的油胺混合，得到第一溶液体系；
S2、氮气排气状态下将第一溶液体系加热至180℃，反应60min，得到包含纳米晶核的溶液体系；
S3、升温，加入24mmol的硬脂酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到纳米晶。
实施例17
磷化铟纳米晶核由In、P、Zn三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟、0.75mmol的Zn-(O-C≡P) 2、10mL的油胺混合，得到第一溶液体系；
S2、氮气排气状态下将第一溶液体系加热至180℃，反应60min，得到包含纳米晶核的溶液体系；
S3、升温，加入24mmol的硬脂酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到纳米晶。
实施例18
磷化铟纳米晶核由In、P、Ga三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、在25℃下，将0.5mmol的氯化铟、0.75mmol的Ga-(O-C≡P) 3、10mL的油胺混合，得到第一溶液体系；
S2、氮气排气状态下将第一溶液体系加热至180℃，反应60min，得到包含纳米晶核的溶液体系；
S3、升温，加入24mmol的硬脂酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到纳米晶。
实施例19
磷化铟纳米晶核由In、P、Na、Zn四种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、在30℃下，将0.5mmol的氯化铟、4.0mmol的氯化锌、0.75mmol的Na-O-C≡P、10mL的油胺混合，得到第一溶液体系；
S2、氮气排气状态下将第一溶液体系加热至180℃，反应60min，得到包含纳米晶核的溶液体系；
S3、升温，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到纳米晶。
对比例8
磷化铟纳米晶核由In、P、Li三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、将0.15mmol的醋酸铟、0.1mmol的乙酸锂、0.1mmol的三(三甲基硅)膦(分散在1mL的TOP中)、0.3mmol的十四酸、10mL的十八烯混合，氮气排气状态下在180℃保温并反应60min，得到包含纳米晶核的溶液体系；
S2、升温，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S3、反应结束，经分离和提纯，得到纳米晶。
对比例9
磷化铟纳米晶核由In、P、Na三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、将0.15mmol的醋酸铟、0.1mmol的乙酸钠、0.1mmol的三(三甲基硅)膦(分散在1mL的TOP中)、0.3mmol的十四酸、10mL的十八烯混合，氮气排气状态下在180℃保温并反应60min，得到包含纳米晶核的溶液体系；
S2、升温，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S3、反应结束，经分离和提纯，得到纳米晶。
对比例10
磷化铟纳米晶核由In、P、Zn三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、将0.15mmol的醋酸铟、0.1mmol的乙酸锌、0.1mmol的三(三甲基硅)膦(分散在1mL的TOP中)、0.3mmol的十四酸、10mL的十八烯混合，氮气排气状态下在180℃保温并反应60min，得到包含纳米晶核的溶液体系；
S2、升温，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S3、反应结束，经分离和提纯，得到纳米晶。
对比例11
磷化铟纳米晶核由In、P、Ga三种元素构成，壳为ZnSe和ZnS构成的双壳层。
磷化铟纳米晶的制备过程如下：
S1、将0.15mmol的醋酸铟、0.1mmol的乙酸镓、0.1mmol的三(三甲基硅)膦(分散在1mL的TOP中)、0.3mmol的十四酸、10mL的十八烯混合，氮气排气状态下在180℃保温并反应60min，得到包含纳米晶核的溶液体系；
S2、升温，加入24mmol的醋酸锌、6mL的硒-三辛基膦溶液(2mmol/mL)并反应，得到包覆在纳米晶核上的ZnSe壳，再加入6mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnSe壳上的ZnS壳；
S3、反应结束，经分离和提纯，得到纳米晶。
图2为实施例15中所述制备的磷化铟纳米晶的透射电子显微镜图，从图中可以看出磷化铟纳米晶的尺寸约在3.5纳米。
图3为实施例15中磷化铟纳米晶的荧光发射光谱图，其荧光发射峰峰值波长约为527纳米，其半峰宽约为37纳米。
此外，进一步测试实施例15至实施例19、对比例8至对比例11中的磷化铟纳米晶的荧光性质。测试结果如下表所示：
  峰值波长(nm) 半峰宽(nm) 量子产率(％)
实施例15 527 37 61
实施例16 531 38 73
实施例17 525 36 74
实施例18 521 40 75
实施例19 530 38 75
对比例8 528 43 41
对比例9 533 45 38
对比例10 524 42 43
对比例11 523 46 36
由如上表格可知，采用M-(O-C≡P) n作为金属元素M和P元素的反应前驱体时，与单独采用M前驱体和P前驱体相比，所制备得到的磷化铟量子点的发射峰峰值波长基本不变，而半峰宽会明显减小，量子产率会明显增加，例如：实施例15与对比例8相比，半峰宽减小6纳米，量子产量增加20％；实施例16与对比例9相比，半峰宽减小7纳米，量子产率增加35％；实施例17与对比例10相比，半峰宽减小6纳米，量子产率增加31％；实施例18与对比例11相比，半峰宽减小6纳米，量子产率增加39％。
青光磷化铟纳米晶的制备
实施例20
青光磷化铟纳米晶1的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、5mmol ZnCl 2、25mL油胺、1mmol Na—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：S2-1、120℃下，于步骤S1的磷化铟纳米晶核溶液中加入10mmol硬脂酸锌，反应30min，形成第一混合液；S2-2、升温至160℃，于步骤S2-1的第一混合液中加入10mmol硫的油胺溶液，反应60min，得到青光磷化铟纳米晶1。
实施例21
青光磷化铟纳米晶2的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、5mmol ZnCl 2、25mL油胺、1mmol Na—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：S2-1、120℃下，于步骤S1的磷化铟纳米晶核溶液中加入8mmol硬脂酸锌，反应30min，形成第一混合液；S2-2、升温至160℃，于步骤S2-1的第一混合液中加入4mmol硒化三辛基膦溶液和4mmol硫化三辛基膦溶液，反应30min，形成第二混合液；S2-3、升温至200℃，于步骤S2-2的第二混合液中加入6mmol醋酸锌，再加入6mmol正十二硫醇，反应60min；S2-4、提高反应体系的温度，进行三次ZnS壳层的生长，得到青光磷化铟纳米晶2。
实施例22
青光磷化铟纳米晶3的制备：
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、10mmol ZnCl 2、25mL油胺、1mmol Na—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：S2-1、120℃下，于步骤S1的磷化铟纳米晶核溶液中加入12mmol二乙基锌，反应30min，形成第一混合液；S2-2、升温至160℃，于步骤S2-1的第一混合液中加入12mmol硒的油胺溶液，反应30min，形成第二混合液；S2-3、升温至180℃，于步骤S2-2的第二混合液中加入6mmol油酸锌，再加入6mmol正十二硫醇，反应60min；S2-4、逐渐提高反应体系的温度，进行三次ZnS壳层的生长，得到青光磷化铟纳米晶3。
实施例23
磷化铟纳米晶核由In、P、Na三种元素构成，第一壳层为ZnS。
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、5mmol ZnCl 2、25mL油胺、1mmol Na—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：S2-1、120℃下，于步骤S1的磷化铟纳米晶核溶液中加入10mmol硬脂酸锌，反应30min，形成第一混合液；S2-2、升温至160℃，于步骤S2-1的第一混合液中加入10mmol硫的油胺溶液，反应60min，得到青光磷化铟纳米晶。
S3、升温到240℃，加入24mmol的醋酸锌、加入12mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnS壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到纳米晶。
实施例24
磷化铟纳米晶核由In、P、K三种元素构成，第一壳层为ZnS。
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、5mmol ZnCl 2、25mL油胺、1mmol K—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：S2-1、120℃下，于步骤S1的磷化铟纳米晶核溶液中加入10mmol硬脂酸锌，反应30min，形成第一混合液；S2-2、升温至160℃，于步骤S2-1的第一混合液中加入10mmol硫的油胺溶液，反应60min，得到青光磷化铟纳米晶1。
S3、升温到240℃，加入24mmol的醋酸锌、加入12mL硫-三辛基膦溶液(2mmol/mL)并反应，得到包覆在ZnS壳上的ZnS壳；
S4、反应结束，经分离和提纯，得到纳米晶。
实施例25
磷化铟纳米晶核由In、P、Na三种元素构成，第一壳层为ZnSeS。
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、5mmol ZnCl 2、25mL油胺、1mmol Na—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：S2-1、120℃下，于步骤S1的磷化铟纳米晶核溶液中加入8mmol硬脂酸锌，反应30min，形成第一混合液；S2-2、升温至160℃，于步骤S2-1的第一混合液中加入4mmol硒化三辛基膦溶液和4mmol硫化三辛基膦溶液，反应30min，形成第二混合液；
S3、升温至240℃，于步骤S2-2的第二混合液中加入6mmol醋酸锌，再加入6mmol正十二硫醇，反应60min；
S4、反应结束，经分离和提纯，得到纳米晶。
实施例26
磷化铟纳米晶核由In、P、K三种元素构成，第一壳层为ZnSeS。
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、5mmol ZnCl 2、25mL油胺、1mmol Na—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：S2-1、120℃下，于步骤S1的磷化铟纳米晶核溶液中加入8mmol硬脂酸锌，反应30min，形成第一混合液；S2-2、升温至160℃，于步骤S2-1的第一混 合液中加入4mmol硒化三辛基膦溶液和4mmol硫化三辛基膦溶液，反应30min，形成第二混合液；
S3、升温至240℃，于步骤S2-2的第二混合液中加入6mmol醋酸锌，再加入6mmol正十二硫醇，反应60min；
S4、反应结束，经分离和提纯，得到纳米晶。
对比例12
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、8mmol ZnI 2、25mL油胺、1mmol Na—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：在240℃下，于步骤S1的磷化铟纳米晶核溶液中加入6mmol硬脂酸锌的十八稀溶液，再加入6mmol硫化三辛基膦溶液，反应60min。
S3、反应结束，经分离和提纯，得到纳米晶30。
对比例13
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、8mmol ZnI 2、25mL油胺、1mmol K—O—C≡P混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：在240℃下，于步骤S1的磷化铟纳米晶核溶液中加入6mmol硬脂酸锌的十八稀溶液，再加入6mmol硫化三辛基膦溶液，反应60min。
S3、反应结束，经分离和提纯，得到纳米晶31。
对比例14
S1、获得磷化铟纳米晶核溶液：在惰性气体氛围下，使1mmol InCl 3、8mmol ZnI 2、25mL油胺、4mmol三(二乙基氨基)膦混合混合，在120℃下反应60min，得到磷化铟纳米晶核溶液；
S2、为磷化铟纳米晶核包覆壳层：在240℃下，于步骤S1的磷化铟纳米晶核溶液中加入6mmol硬脂酸锌的十八稀溶液，再加入6mmol硫化三辛基膦溶液，反应60min。
S3、反应结束，经分离和提纯，得到纳米晶。
测试表征：分别将实施例20到实施例26中获得的青光磷化铟纳米晶、对比例12至对比例14获得的磷化铟纳米晶分散在甲苯溶液中，测试其荧光光谱和荧光量子产率。具体测试结果如下表所示。
Figure PCTCN2020085274-appb-000003
Figure PCTCN2020085274-appb-000004
根据上表可知，本申请能够成功制备出青光磷化铟纳米晶，其荧光量子产率高，从而证明通过本申请制备方法获得的青光磷化铟纳米晶具有优良的发光性能，从而拓宽了磷化铟纳米晶的应用使用范围。
尽管发明人已经对本申请的技术方案做了较详细的阐述和列举，应当理解，对于本领域技术人员来说，对上述实施例作出修改和/或变通或者采用等同的替代方案是显然的，都不能脱离本申请精神的实质，本申请中出现的术语用于对本申请技术方案的阐述和理解，并不能构成对本申请的限制。

Claims (26)

  1. 一种磷化铟纳米晶的制备方法，其特征在于，包括步骤：采用M-(O-C≡P) n作为反应前驱体之一，其中，M为金属元素，n为M元素的化合价价态值。
  2. 根据权利要求1所述的制备方法，其特征在于，所述反应前驱体还包括铟前驱体；优选地，所述反应前驱体还包括锌前驱体。
  3. 根据权利要求1所述的制备方法，其特征在于，所述磷化铟纳米晶含有M、In和P元素，以及可选的Zn元素。
  4. 根据权利要求1所述的制备方法，其特征在于，包括步骤：对包含有铟前驱体、M-(O-C≡P) n、可选的锌前驱体和溶剂的溶液进行高温处理，得到磷化铟纳米晶核，所述高温处理的温度为150～340℃之间，优选为150～300℃之间。
  5. 根据权利要求4所述的制备方法，其特征在于，包括步骤：在所述纳米晶核上包覆壳层；优选地，所述溶剂为配位化合物；优选地，所述配位化合物为胺或者羧酸。
  6. 一种磷化铟纳米晶，其特征在于，所述磷化铟纳米晶由权利要求1至5中任一项所述的制备方法制得。
  7. 一种近红外磷化铟纳米晶的合成方法，其特征在于，包括以下步骤：
    S1、获得包含铟前驱体及可选的锌前驱体的第一溶液体系、包含M-(O-C≡P) n作为磷前驱体的第二溶液体系；S2、在预定温度下，使所述第一溶液体系与所述第二溶液体系混合并反应，得到所述近红外磷化铟纳米晶；所述第一溶液体系包括所述铟前驱体、可选的所述锌前驱体和分散所述铟前驱体的第一有机溶剂，所述第二溶液体系包括所述磷前驱体和分散所述磷前驱体的第二有机溶剂，所述第一有机溶剂与所述第二有机溶剂不相同，所述第二有机溶剂的沸点低于所述的预定温度。
  8. 根据权利要求7所述的制备方法，其特征在于，所述第二有机溶剂的沸点比所述的预定温度低至少30℃；优选地，所述合成方法还包括步骤S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质，在所述近红外磷化铟纳米晶表面形成壳体，以使所述近红外磷化铟纳米晶的荧光发射峰峰值在700～900nm。
  9. 根据权利要求7所述的制备方法，其特征在于，所述预定温度的范围为180～320℃；优选地，所述第二有机溶剂的沸点小于等于150℃，优选为60～150℃；优选所述第二有机溶剂包括苯、甲苯、环己烷、正己烷、正庚烷、正辛烷、四氢呋喃、氯仿中的至少一种。
  10. 根据权利要求7所述的制备方法，其特征在于，所述铟前驱体为卤化铟。
  11. 根据权利要求7所述的制备方法，其特征在于，所述第一有机溶剂为碳原子数≥6的饱和或者不饱和胺，或者羧酸中的至少一种；优选地，所述第一溶液体系中还包括所述锌前驱体。
  12. 根据权利要求7所述的制备方法，其特征在于，所述纳米晶的壳包括ZnS、ZnSe、ZnSeS中的至少一种。
  13. 一种近红外磷化铟纳米晶，其特征在于，所述近红外磷化铟纳米晶由权利要求7至12中任一项所述的制备方法制得；优选地，所述磷化铟纳米晶的发射峰峰值在在700～900nm。
  14. 一种红光磷化铟纳米晶的制备方法，其特征在于，包括步骤：
    S1、使铟前驱体、磷前驱体M-(O-C≡P) n与有机溶剂混合，于第一温度下反应，得到 磷化铟纳米晶核溶液；S2、将所述磷化铟纳米晶核溶液迅速升温至第二温度；S3、于S2的反应体系中加入合成纳米晶的壳所需的前体物质，得到所述红光磷化铟纳米晶，所述红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。
  15. 根据权利要求14所述的制备方法，其特征在于，所述第一温度的范围在110～160℃；优选地，所述第二温度的范围在280～340℃。
  16. 根据权利要求14所述的制备方法，其特征在于，S2中，将所述磷化铟纳米晶核溶液迅速升温至第二温度，保持至少10min。
  17. 根据权利要求14所述的制备方法，其特征在于，所述有机溶剂选自碳原子数≥6的饱和或者不饱和胺、或者羧酸中的至少一种。
  18. 根据权利要求14所述的制备方法，其特征在于，所述磷化铟纳米晶核溶液中可选地含有第一锌前驱体，所述第一锌前驱体选自卤化锌。
  19. 根据权利要求14所述的制备方法，其特征在于，所述纳米晶的壳包括ZnS、ZnSe、ZnSeS中的至少一种。
  20. 一种红光磷化铟纳米晶，其特征在于，所述红光磷化铟纳米晶由权利要求14到19中任一项所述的制备方法制得，所述红光磷化铟纳米晶的荧光发射峰峰值在580～670nm。
  21. 一种青光磷化铟纳米晶的制备方法，其特征在于，包括步骤：
    S1、使铟前驱体、磷前驱体M-(O-C≡P) n与有机溶剂混合，于第一温度下反应，得到磷化铟纳米晶核溶液；S2、在所述第一温度下，于所述磷化铟纳米晶核溶液中加入锌的阳离子前体，形成第一混合液；S3、第二温度下，于所述第一混合液中加入硫或硒阴离子前体，所述阳离子前体与所述阴离子前体反应为磷化铟纳米晶核包覆壳层，得到所述青光磷化铟纳米晶，所述青光磷化铟纳米晶的荧光发射峰峰值在460～500nm；其中，所述第二温度大于所述第一温度。
  22. 根据权利要求21的制备方法，其特征在于，所述第一温度的范围在110～160℃，所述第二温度的范围在160～240℃，优选为160～200℃。
  23. 根据权利要求21的制备方法，其特征在于，所述有机溶剂选自碳原子数≥6的饱和或者不饱和胺、或羧酸中的至少一种；优选地，所述磷化铟纳米晶核溶液中可选的含有第一锌前驱体，所述第一锌前驱体选自卤化锌。
  24. 根据权利要求21所述的制备方法，其特征在于，以物质的量计，步骤S2中的所述锌的阳离子前体与步骤S1中所述的铟前驱体的比值为(8～40):1；优选地，所述锌的阳离子前体选自羧酸锌、或者有机锌试剂。
  25. 根据权利要求21所述的制备方法，其特征在于，所述阴离子前体为硫前体、硒前体中的至少一种。
  26. 一种青光磷化铟纳米晶，其特征在于，所述青光磷化铟纳米晶由权利要求21到25中任一项所述的制备方法制得，所述青光磷化铟纳米晶的荧光发射峰峰值在460～500nm。
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