WO2017201967A1 - Iii-v族量子点、其制备方法及其应用 - Google Patents

Iii-v族量子点、其制备方法及其应用 Download PDF

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WO2017201967A1
WO2017201967A1 PCT/CN2016/104257 CN2016104257W WO2017201967A1 WO 2017201967 A1 WO2017201967 A1 WO 2017201967A1 CN 2016104257 W CN2016104257 W CN 2016104257W WO 2017201967 A1 WO2017201967 A1 WO 2017201967A1
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iii
quantum dot
group
group iii
seed crystal
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彭笑刚
李洋
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Zhejiang University ZJU
Najing Technology Corp Ltd
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Zhejiang University ZJU
Najing Technology Corp Ltd
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Definitions

  • the invention relates to the field of quantum dot materials, in particular to a group III-V quantum dot, a preparation method thereof and an application thereof.
  • Quantum dots are widely used in optoelectronic devices due to their narrow, tunable luminescence properties.
  • III-V quantum dots have become the focus of research and development of II-VI quantum dots in recent years because they do not contain cadmium.
  • the currently widely used III-V quantum dot preparation method is a thermal injection method, and the group III element precursor and the group V element precursor are grown and matured at a high temperature.
  • TMS3P tris(trimethylsilyl)phosphine
  • the thermal injection method is suitable for the synthesis of II-VI quantum dots, but not for the III-V quantum dot synthesis.
  • the main object of the present invention is to provide a group III-V quantum dot, a preparation method thereof and an application thereof, to solve the problem that it is difficult to obtain a group III-V quantum dot having a uniform size distribution in the prior art method.
  • a method for preparing a III-V group quantum dot which comprises: S1, a Group III element precursor, a solvent, a surfactant, a III-V group
  • the quantum dot seed crystal is mixed to obtain a mixed system; S2, heating the mixed system to the first temperature; and S3, adding the group V element precursor to the mixed system having the temperature of the first temperature to obtain a III-V group quantum dot, wherein
  • the surface of the III-V quantum dot seed crystal carries a carboxylic acid ligand, the surfactant is a derivative of acetylacetone or acetylacetone or a compound having a carboxylic acid group RCOOH, and the first temperature is between 120 ° C and 200 ° C.
  • P1 and P2 are each independently selected from the group consisting of an alkyl group, an alkyl group having a substituent, an alkenyl group, an alkenyl group having a substituent, and an aryl group.
  • the first temperature is between 140 and 180 °C.
  • n is an integer of 0 to 4.
  • R in the above RCOOH is a saturated hydrocarbon group having a carbon number of ⁇ 6, and preferably RCOOH is acetic acid, propionic acid or isopropyl acid.
  • the concentration of the above surfactant in the mixed system is from 0.025 to 0.125 mol/L.
  • step S3 comprises batch adding the group V element precursor to the mixed system.
  • group III element precursor is A(B) 2 C, A(C) 3 or A(D) 3 , wherein A is a group III element, B is a fatty acid radical having a carbon number of ⁇ 8, and C is carbon.
  • carboxylic acid ligand is a carboxylate ligand having a carbon number of ⁇ 8, preferably an octoate, citrate, tetradecanoate, stearate or oleate.
  • a Group III-V quantum dot having a relative standard deviation of a particle size distribution of ⁇ 10%.
  • a core-shell nanocrystal comprising a core and a shell layer, the core being a III-V quantum dot prepared by the above preparation method or the above-mentioned III-V quantum dot,
  • the shell layer includes a Group IIB-VI element or a Group III-V element.
  • composition comprising a group III-V quantum dot which is a group III-V quantum dot prepared by the above preparation method or the above III- Group V quantum dots.
  • a quantum dot film comprising a III-V group quantum dot which is a III-V quantum dot prepared by the above preparation method or the above III -V family of quantum dots.
  • an electroluminescent device comprising a luminescent substance comprising a group III-V quantum dot, the group III-V quantum dot being prepared by the above preparation method III- Group V quantum dots or Group III-V quantum dots as described above.
  • the seed crystal provides a nucleation site, and under thermal perturbation, the surfactant partially replaces the original ligand on the surface of the seed crystal because the binding ability of the original carboxylic acid ligand to the surface of the seed crystal is better.
  • the bulk reactant can grow on the seed instead of self-nucleating, because the self-nucleation energy barrier grows higher than the seed crystal, so it can separate the nucleation and growth, which is beneficial to the III-V quantum dot nanocrystal. Growth.
  • the above reaction temperature is controlled above 120 ° C and below 200 ° C, the group III element can be effectively avoided.
  • the group V elements do not grow on the surface of the seed crystal but independently generate nuclei, which affect the particle size distribution.
  • the above reaction temperature is controlled between 120 and 200 ° C.
  • the III-V quantum dot seed crystals are effectively prevented from being oxidized, on the other hand, the volatilization of the surfactant is reduced, the raw material usage is saved, and the environment is more environmentally friendly.
  • FIG. 1 shows a UV-vis test for detecting UV-visible absorption and emission peaks of InP quantum dots obtained by treating different surfactants and no surfactant treatment according to Examples 1, 5 to 10 of the present invention, wherein long lines indicate ultraviolet rays. Visible absorption peaks, short lines indicate UV-visible emission peaks;
  • FIG. 2 is a schematic diagram showing the first exciton peak of InP quantum dots obtained by the treatment of different surfactant treatments according to Examples 1, 5 to 10 of the present invention by UV-vis test;
  • FIG. 3 is a schematic diagram showing the ultraviolet absorption of InP quantum dots obtained by different In precursors and ligands according to Examples 1, 11 to 13, 23 and 24 of the present invention by UV-vis test;
  • FIG. 4 is a schematic diagram showing the ultraviolet absorption of InP quantum dots obtained at different temperatures according to Examples 1, 14 to 19 of the present invention by UV-vis test;
  • FIG. 5 is a schematic diagram showing the ultraviolet absorption of InP quantum dots obtained by using UV-vis test to detect different surfactant concentrations according to Examples 1, 20 to 22 of the present invention
  • Fig. 6 (a) and (b) are views showing the ultraviolet absorption spectrum and the fluorescence emission spectrum of the core-shell quantum dots of different sizes obtained according to Example 13 of the present invention by UV-vis test and fluorescence spectrometer, Fig. 6 (d) Schematic diagrams of UV absorption spectra of InP quantum dots, InAs quantum dots and InAs/InP quantum dots in the presence or absence of a surfactant, respectively;
  • Example 7 is a transmission electron microscopy test chart and particle size distribution diagram of a seed crystal prepared in Example 2 and reacted with Example 1 for 20 min according to the present application, wherein (a) is a seed crystal prepared in Example 2.
  • Figure 9 shows the effect of using acetic acid and no acetic acid on the synthesis size of the seed crystals using UV-vis.
  • the following preparation methods are the same as those in the prior art for preparing a quantum dot to a reaction environment unless otherwise specified, and the atmosphere in the reactor is removed by using an inert gas atmosphere or an air atmosphere in which moisture and oxygen are removed before the reaction.
  • Oxygen wherein the inert gas is nitrogen, argon or a rare gas.
  • the quantum dot size distribution in the prior art is wide, and the performance thereof is affected. Specifically, if each quantum dot in the quantum dot group produced is different in size, it means photoelectric conversion performance. Different, then the application of this quantum dot group is limited. For example, blue light excites a quantum dot to generate red light, and a quantum dot produces green light. However, the best effect is that blue light excites each quantum dot to generate a kind of light. the same.
  • a method for preparing a group III-V quantum dot which comprises: S1, a group III element precursor, a solvent, a surfactant, Group III-V quantum dot seed crystals are mixed to obtain a mixed system; S2, heating the mixed system to a first temperature; and S3, adding a group V element precursor to the mixed system at a temperature of the first temperature to obtain a III-V group quantum
  • the III-V quantum dot seed crystal carries a carboxylic acid ligand
  • the surfactant is a derivative of acetylacetone or acetylacetone or a compound having a carboxylic acid group RCOOH
  • the first temperature is 120 ° C to 200 Between ° C, the above derivatives have the following structural formula: Wherein P1 and P2 are each independently selected from the group consisting of an alkyl group, an alkyl group having a substituent, an alkenyl group, an alkenyl group having a substituent, an alkenyl group, an alkenyl group having
  • group III element precursor, the solvent, the surfactant, and the group III-V quantum dot seed crystal are not chemically reacted prior to the addition of the group V element precursor, the group III element precursor, solvent, surfactant, and There is no specific order for the addition of group III-V quantum dot seed crystals. In order to better contact the substances with each other, it is preferred to mix the group III element precursor, the solvent and the surfactant, and then add the group III-V quantum dots thereto. Seed crystals to obtain the mixed system.
  • the seed crystal provides a nucleation site
  • the surfactant partially replaces the original ligand on the surface of the seed crystal, because the binding ability of the original ligand to the surface of the seed crystal is strong, which hinders
  • the combination of free monomers on the surface of the seed crystal, and the ability of the surfactant to bind to the surface of the seed crystal is weak, that is, the surfactant has a fast switching ability to the surface of the crystal and the unbound state, so that the free monomer reactant is Growth on seed crystals rather than self-nucleation, because self-nucleation energy barriers grow higher than on seed crystals, so nucleation and growth can be separated, which in turn facilitates the growth of III-V quantum dot nanocrystals.
  • the group III element and the group V element are grown on the surface of the seed crystal, and the surface activator etches the surface of the crystal after the growth to achieve the activation purpose, and promotes the growth of more group III elements and group V elements. Go to the surface of the crystal to achieve crystal growth.
  • the surfactant is a compound having a carboxylic acid group RCOOH
  • the surface activator loses a proton
  • the carboxylic acid ligand of the III-V quantum dot seed crystal will obtain a proton, and the surfactant becomes a III-V quantum dot.
  • the ligand of nanocrystals through this ligand exchange, the surface carboxylic acid ligand and the free acid reach a dynamic equilibrium, this surface activation can avoid the formation of group III element-O bond on the surface of group III-V quantum dots, which is beneficial to The growth of III-V quantum dot nanocrystals on the surface of the seed crystal forms a III-V quantum dot with uniform particle size distribution.
  • the surfactant is acetylacetone and its derivatives
  • part of acetylacetone and its derivatives are converted into acetylacetone and its derivative ligands, and the exchange with carboxylic acid ligands is completed, so that III-V
  • the absorption of the quantum dot seed crystals is blue-shifted, and the purpose of etching the III-V quantum dot seed crystals is achieved.
  • the bidentate-supported group III-V quantum dot seed crystals have a small steric hindrance due to the bidentate coordination, so that the subsequently added V group element precursor can effectively react with the group III precursor in the system.
  • the surface of the seed crystal continues to grow, and the self-nucleation phenomenon of the group III precursor and the group V precursor is inhibited, thereby forming a group III-V quantum dot having a uniform particle size distribution.
  • the above reaction temperature is controlled above 120 ° C, the group III element and the group V element can be effectively prevented from growing on the surface of the seed crystal, but the core is formed independently, and the particle size distribution is affected.
  • the above reaction temperature is controlled between 120 and 200 ° C.
  • the III-V quantum dot seed crystals are effectively prevented from being oxidized, on the other hand, the volatilization of the surfactant is reduced, the raw material usage is saved, and the environment is more environmentally friendly.
  • the first temperature is between 140 and 180 ° C, which is more advantageous for controlling the particle size distribution of the obtained quantum dots.
  • the above derivative has the following structural formula: Wherein m is an integer of 0 to 4, and n is an integer of 0 to 4.
  • the particle size of the III-V quantum dots obtained by the above preparation method can be controlled by the addition amount of the V group element precursor.
  • the above S3 includes adding the V group element precursors to the mixed system in batches. The amount and number of additional additions are determined based on the ultraviolet first exciton peak of the III-V quantum dots.
  • the surfactant is RCOOH, wherein R is a carbon number ⁇ 6 saturated hydrocarbon group, preferably RCOOH is acetic acid, propionic acid or isopropyl acid. Since the above alkyl acid has a moderate carbon chain length and a small steric hindrance, it can be exchanged with the ligand of the seed crystal more quickly.
  • the group III element precursor of the present application may be any one of A(B) 2 C, A(C) 3 or A(D) 3 , wherein A is a group III element, B is a fatty acid group, and C is a carbon number. ⁇ 6 fatty acid radicals or CH 3 COCH 2 COCH 2 -, D is a halogen ion, and the V group precursor may be (trimethylsilyl)phosphorus (TMS 3 P), tris(triethylsilyl)phosphorus (TES) 3 P) and tris(trimethylsilyl) arsenic (TMS 3 As), the solvent in the step S1 may be a non-coordinating solvent, such as a long-chain fatty alkane or a long-chain aliphatic olefin, preferably Tetradecane or octadecane.
  • a non-coordinating solvent such as a long-chain fatty alkane or a long-chain aliphatic olefin, preferably Tetrade
  • the surface activator in the present application is mainly for providing a group exchanged with a carboxylic acid ligand of a group III-V quantum dot seed crystal.
  • a surfactant is preferably used in the mixed system.
  • the concentration is 0.025 to 0.125 mol/L.
  • the concentration is less than 0.025 mol/L, and the etching effect is small, but if the concentration is increased to 0.125 mol/L, if it continues to increase, it does not bring about an increase in the growth rate.
  • the higher concentration is also possible to react. Since there is no significant increase in growth rate, the highest concentration is controlled at 0.125 mol/L from the viewpoint of saving raw materials and improving efficiency.
  • some low-boiling surfactants may have a certain degree of volatilization, and in order to ensure sufficient surfactant in the whole reaction, the concentration of the surfactant may be appropriately increased.
  • the preferred ligand is a carboxylate ligand having 18 ⁇ carbon number ⁇ 8, such as octoate, citrate, tetradecanoate, stearate Or oleate. Since the steric hindrance of the carboxylic acid ligand carbon chain is large, due to its large steric hindrance, the substituted carboxylic acid hinders the continued growth of the quantum dots, and thus cannot synthesize large-sized quantum dots.
  • the surface of the seed crystal can be first exchanged for the surface carboxylic acid ligand of the III-V seed crystal, thereby activating the surface of the seed crystal, thereby promoting the uniform growth of the subsequently added V group precursor.
  • the synthesis of uniform III-V quantum dots can be achieved well.
  • the Group III-V quantum dot seed crystals used in the present application can be produced by a method of synthesizing seed crystals in the prior art.
  • the seed crystal synthesis method is based on an alkylamine method and an alkylamine as a ligand, which can increase the reactivity of the group III precursor, lower the reaction temperature, thereby inhibiting the formation of indium oxide on the surface of the seed crystal, and facilitating subsequent monomer reaction.
  • the growth of the object on the surface of the seed crystal The inventors found through experiments that when the In precursor is reacted with In(Ac) 3 and myristic acid to form InMy 2 Ac during the seed crystal synthesis, the reaction also generates acetic acid, and the reaction product system is argon gas for 20 min.
  • a group III-V quantum dot is provided, and the relative standard deviation (RSD) of the particle size distribution of the group III-V quantum dots is ⁇ 10%. Since the particle size distribution of the quantum dots is narrow, the half-width of the fluorescence emission spectrum can still be maintained at about 40 nm, and the narrower the half-peak width, the sharper the peak shape and the purer the color.
  • the III-V group quantum dots can be prepared by the above preparation method.
  • a core-shell nanocrystal is further provided, the core-shell nanocrystal comprising a core and a shell layer, wherein the core is the III-V quantum dot, the shell layer Includes Group IIB-VI or Group III-V elements.
  • the shelling process can be performed using existing techniques.
  • III-V group quantum dots prepared in the present application have excellent photoelectric properties because of a narrow half-peak width and high uniformity. It can be used in quantum dot compositions, such as bio-detection, solar energy, display, illumination, etc.; it can be used as a quantum dot film as a light conversion device to improve the color gamut of the display, and can also be used as a light-emitting device in an electroluminescent device. Substance, an organic luminescent substance that replaces an organic electroluminescent device.
  • Tris(trimethylsilyl)phosphine (TMS 3 P, 10 wt% in hexane, >98%), tris(triethylsilyl)phosphine (TES 3 P in hexane, 10 wt%, > 98%), tris(trimethylsilyl)arsenic (TMS 3 As, 10% by weight in hexane, >98%) was synthesized by Najing Technology Co., Ltd.
  • TMS 3 P, TES 3 P, TMS 3 As were distilled before use and stored in a glove box.
  • the method was synthesized with InMy 2 Ac except that HMy was replaced with HDe or HSt.
  • De - St ligand or 500nm InP seed synthesis synthesis with My - InP seed ligand, but replaced with HMy HDe or HSt.
  • a mixture of 0.15 mmol of InMy 2 Ac and 2.5 ml of tetradecane was placed in a 25 ml flask. After bubbling the mixture with Ar gas for 10 min, 0.3 mmol of Hacac was injected into the mixture to obtain an initial mixed system, and the initial mixed system was heated to 160 ° C to obtain an initial hot mixing system. Adding 2 ⁇ 10 -7 mol of InP seed with My-ligand (about 1.5 ml) to the initial hot mixing system to obtain a mixed system (the concentration of surfactant Actacac in the mixed system is 0.075 mol/L), The mixed system was heated to 160 ° C to obtain a hot mixed system.
  • Example 2 The system containing InP quantum dots of different wavelengths obtained in Example 1 was cooled to 150 ° C, 0.2 mmol of octanoic acid was injected into the system, and after 5 min, a certain amount of zinc oleate ODE solution (0.2 mM) was added to the system, and the temperature was raised. To 260 ° C, then add the same amount of TOPSe solution to zinc oleate and keep the reaction for 30 min. At the same time, the fluorescence emission spectrum of InP/ZnSe quantum dots obtained after 30 min reaction was detected by PL spectroscopy. The specific detection results are shown in Fig. 6(b).
  • In-situ purification of InAs seed crystals The procedure was the same as in Example 2 except that, in addition to the first time, 0.15 ml of oleylamine was added after the addition of methanol. For the second time, only hexane and methanol were added.
  • a mixture of 0.15 mol of InDe 2 Ac and 2.5 ml of tetradecane was added to 25 ml, and the mixture was placed in a flask. After bubbling the mixture with Ar gas for 10 min, 0.3 mmol of HAc was injected into the mixture to obtain an initial mixed system, and the initial mixed system was heated to 160 ° C to obtain an initial hot mixing system.
  • 2 ⁇ 10 -7 mol of the InAs seed crystal (about 1.0 ml) with the My-ligand purified in Example 3 was injected to obtain a mixed system (the concentration of the surfactant HAc in the mixed system was 0.075). Mol/L), the mixed system was heated to 160 ° C to obtain a hot mixed system.
  • the synthesis was carried out in the same manner as in Example 1, except that Haac was sequentially replaced with HAc, HHe, HDe, HMy and HSt, 2,4-decanedione.
  • UV-vis test was used to detect the emission peak of InP quantum dots obtained after 20 minutes of reaction.
  • the specific detection results are shown in Fig. 1.
  • the emission peaks of InP quantum dots obtained by different reaction time were detected by UV-vis test.
  • the specific detection results are shown in Fig. 2. , in which the results of 2,4-nonanedione and Hacac coincide.
  • Example 3 Same synthesis method as in Example 1, except that the precursor InMy 2 Ac successively replaced InDe 2 Ac, InSt 2 Ac and InMy 2 acac. At the same time, the UV-vis test was used to detect the emission peak of the InP quantum dots obtained after 20 minutes of reaction. The specific detection results are shown in Fig. 3.
  • the synthesis method was the same as that in Example 1.
  • the reaction temperature was 120 ° C, 140 ° C, 180 ° C, and 200 ° C, and the emission peak of the InP quantum dots obtained by the reaction for 20 min was detected by UV-vis test.
  • the specific detection results are shown in FIG. 4 .
  • the synthesis method was the same as that in Example 1.
  • the concentration of the surfactant Haacac in the mixed system was 0.025 mol/L, 0.075 mol/L, and 0.125 mol/L, respectively, and the emission of InP quantum dots was detected by UV-vis test for 20 min. Peak, the specific test results are shown in Figure 5.
  • the synthesis method was the same as that in Example 1, except that the seed crystal was sequentially replaced with a De - ligand 500 nm InP seed crystal, a St - ligand 500 nm InP seed crystal, and a UV-vis test was used to detect the emission peak of the InP quantum dot obtained by the reaction for 20 min.
  • the specific test results are shown in Figure 3.
  • Quantum dots of Comparative Example 1 were obtained in the same manner as in Example 1, except that no seed surfactant was added.
  • Example 7 The seed crystal of the above Example 2 was reacted with Example 3 for 20 min to obtain an InP quantum dot whose size was measured by X-ray diffraction (XRD), wherein the instrument was a qualitative Ultimate-IV X-ray diffractometer, and the test condition was 40 kV/40 mA using Cu K ⁇ . line
  • XRD X-ray diffraction
  • the quantum dots were centrifuged with acetone and placed on a glass substrate for testing. The test results are shown in Figure 7.
  • Example 2 The seed crystals prepared in Example 2 were reacted with Example 1 and Comparative Example 1 for 20 min to obtain quantum dots, which were examined by transmission electron microscopy, and the results are shown in Figs. 7 and 8.
  • FIG. 6 shows the ultraviolet absorption spectrum of the InP quantum dots of the ultraviolet first exciton peak of 500 to 650 nm, and (b) shows the fluorescence emission of the InP/ZnSe quantum dots of the emission peak of 500 to 700 nm (PL).
  • the spectrum, (d) is shown as an ultraviolet absorption spectrum of InAs and InP grown with or without Inactor.
  • FIG. 7 is a transmission electron micrograph of the InP seed crystal, which has a size of 1.97 nm and an RSD of about 14.5%.
  • (b) shows a transmission electron micrograph of the InP seed crystal grown, the size of which is 3.84nm, the RSD is about 6.7%,
  • (c) shows that the crystal structure of the obtained quantum dot is a sphalerite structure, and
  • (d) shows that the standard deviation of the particle size is 6.7%, reaching the level of the general II-VI quantum dot. It is indicated that the particle size distribution of the III-V quantum dots obtained in the present application is narrow.
  • the quantum dot shape obtained in Comparative Example 1 is non-uniform, and the addition of the V group element precursor quantum dots does not grow.
  • the seed crystal provides a nucleation site, and under thermal perturbation, the surfactant partially replaces the original ligand on the surface of the seed crystal, because the original carboxylic acid ligand has strong binding ability to the surface of the seed crystal.
  • the surfactant has a fast binding and non-binding state switching ability, so that the free monomer reactant can be Growth on seed crystals rather than self-nucleation, because self-nucleation energy barriers grow higher than on seed crystals, so nucleation and growth phases can be separated, which in turn facilitates the growth of III-V quantum dot nanocrystals.
  • the group III element and the group V element are grown on the surface of the seed crystal, and the surface activator etches the surface of the crystal after the growth to achieve the activation purpose, and promotes the growth of more group III elements and group V elements. Go to the surface of the crystal to achieve crystal growth.
  • the surfactant is a compound having a carboxylic acid group RCOOH
  • the surface activator loses a proton
  • the carboxylic acid ligand of the III-V quantum dot seed crystal will obtain a proton, and the surfactant becomes a III-V quantum dot.
  • the ligand of nanocrystals through this ligand exchange, the surface carboxylic acid ligand and the free acid reach a dynamic equilibrium, this surface activation can avoid the formation of group III element-O bond on the surface of group III-V quantum dots, which is beneficial to The growth of III-V quantum dot nanocrystals on the surface of the seed crystal forms a III-V quantum dot with uniform particle size distribution.
  • the surfactant is acetylacetone and its derivatives
  • part of acetylacetone and its derivatives are converted into acetylacetone and its derivative ligands, and the exchange with the carboxylic acid ligand is completed, so that III-
  • the absorption of the V-type quantum dot seed crystals is blue-shifted, and the purpose of etching the III-V quantum dot seed crystals is achieved, and the double-dentate coordinated III-V quantum dot seed crystals are obtained, which has a small space due to the bidentate coordination.
  • the steric hindrance enables the subsequent addition of the group V element precursor to effectively react with the group III precursor in the system, continue to grow on the surface of the seed crystal, and inhibit the self-nucleation of the group III precursor and the group V precursor. Thereby, a group III-V quantum dot having a uniform particle size distribution is formed.
  • the above reaction temperature is controlled between 120 and 200 ° C.
  • the III-V quantum dot seed crystals are effectively prevented from being oxidized, on the other hand, the volatilization of the surfactant is reduced, the raw material usage is saved, and the environment is more environmentally friendly.

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Abstract

本发明提供了III-V族量子点、其制备方法及其应用。该制备方法包括：S1，将III族元素前体、溶剂、表面活化剂、III-V族量子点晶种混合，得到混合体系；S2，加热混合体系至第一温度；以及S3，向温度为第一温度的混合体系中加入V族元素前体，得到III-V族量子点，其中，III-V族量子点晶种表面带有羧酸配体，表面活化剂为乙酰丙酮或乙酰丙酮的衍生物或带有羧酸基团的化合物RCOOH，第一温度为120℃～200℃之间。将上述反应温度控制在120℃以上，200℃以下，晶种提供了成核位点，因为自成核的能垒比在晶种上生长更高，因此可以使成核和生长阶段分开，进而利于III-V族量子点的生长而影响粒径分布。

Description

III-V族量子点、其制备方法及其应用 技术领域
本发明涉及量子点材料领域，具体而言，涉及一种III-V族量子点、其制备方法及其应用。
背景技术
量子点由于其具有窄的、可调的发光特性被广泛应用于光电器件中。其中III-V族量子点由于不含镉，近年来成为继II-VI族量子点的研发重点。目前广泛采用的III-V族量子点制备方法是热注入法，III族元素前体和V族元素前体在高温下生长成熟。但是由于三(三甲基硅基)膦(TMS3P)的活性高和羧酸铟前体中杂质水的存在使得很难平衡成核和生长，因此量子点的尺寸分布变宽。由此可见，热注入法适用于II-VI族量子点合成，但不适用于III-V族量子点合成。
另外，热注入法也难以生成大尺寸的III-V族量子点。Cossairt等人采用In(Ac)3和十八烷基磷酸合成了尺寸分布窄的InP魔幻尺寸纳米簇，但是反应温度高达到370摄氏度。还有一些团队尝试通过P前体的结构来降低P前体转换速率，但最近被证实降低前体转换速率无法优化尺寸分布。
利用传统的晶种法也难以得到高质量的III-V族量子点，其困难在于晶种表面的III族元素的氧化物阻止自由单体在晶种表面生长。
发明内容
本发明的主要目的在于提供一种III-V族量子点、其制备方法及其应用，以解决现有技术中的方法难以得到尺寸分布均匀的III-V族量子点的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种III-V族量子点的制备方法，该制备方法包括：S1，将III族元素前体、溶剂、表面活化剂、III-V族量子点晶种混合，得到混合体系；S2，加热混合体系至第一温度；以及S3，向温度为第一温度的混合体系中加入V族元素前体，得到III-V族量子点，其中，III-V族量子点晶种表面带有羧酸配体，表面活化剂为乙酰丙酮或乙酰丙酮的衍生物或带有羧酸基团的化合物RCOOH，第一温度为120℃～200℃之间，上述衍生物具有以下结构式：
Figure PCTCN2016104257-appb-000001
其中，P1和P2分别独立地选自烷基、具有取代基的烷基、烯基、具有取代基的烯基和芳基中的任意一种基团。
进一步地，上述第一温度在140～180℃之间。
进一步地，上述衍生物具有以下结构式：
Figure PCTCN2016104257-appb-000002
其中，m为0～4的整数，n为0～4的整数。
进一步地，上述RCOOH中的R是碳数≤6饱和烃基，优选RCOOH为乙酸、丙酸或异丙酸。
进一步地，上述表面活化剂在混合体系的浓度为0.025～0.125mol/L。
进一步地，上述步骤S3包括将V族元素前体分批加入混合体系中。
进一步地，上述III族元素前体为A(B)2C、A(C)3或A(D)3，其中，A为III族元素，B为碳数≥8的脂肪酸根，C为碳数≤6的脂肪酸根或CH3COCH2COCH2-，D为卤素离子。
进一步地，上述羧酸配体为碳数≥8的羧酸盐配体，优选辛酸盐、癸酸盐、十四酸盐、硬脂酸盐或油酸盐。
根据本发明的另一方面，提供了一种III-V族量子点，该III-V族量子点的粒径分布的相对标准偏差≤10％。
根据本发明的又一方面，提供了一种核壳纳米晶，包括核和壳层，该核为上述的制备方法制备而成的III-V族量子点或上述的III-V族量子点，壳层包括IIB-VI族元素或III-V族元素。
根据本发明的又一方面，提供了一种组合物，包括III-V族量子点，该III-V族量子点为上述的制备方法制备而成的III-V族量子点或上述的III-V族量子点。
根据本发明的又一方面，提供了一种量子点膜，包括III-V族量子点，该III-V族量子点为上述的制备方法制备而成的III-V族量子点或上述的III-V族量子点。
根据本发明的再一方面，提供了一种电致发光器件，包括发光物质，该发光物质包括III-V族量子点，该III-V族量子点为上述的制备方法制备而成的III-V族量子点或上述的III-V族量子点。
应用本发明的技术方案，晶种提供了成核位点，在热扰动下，表面活化剂部分替换晶种表面的原有配体，因为原有羧酸配体与晶种表面的结合能力较强，会阻碍自由单体在晶种表面的结合，而表面活化剂与晶种表面的结合能力较弱，即表面活化剂具有快速与晶体表面结合和非结合状态的切换能力，使得自由的单体反应物可以在晶种上生长而不是自成核，因为自成核的能垒比在晶种上生长更高，因此可以使成核和生长分开，进而利于III-V族量子点纳米晶的生长。同时，将上述反应温度控制在120℃以上，200℃以下，可以有效避免III族元素 和V族元素不在晶种表面上生长而是独立生成核，而影响粒径分布。将上述反应温度控制在120～200℃之间，一方面有效避免III-V族量子点晶种被氧化，另一方面减少表面活化剂的挥发，节约原料使用量，且更为环保。
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示出了采用UV-vis测试检测根据本发明实施例1、5至10不同表面活化剂处理及无表面活化剂处理得到的InP量子点的紫外可见吸收和发射峰示意图，其中长线表示紫外可见吸收峰，短线表示紫外可见发射峰；
图2示出了采用UV-vis测试检测根据本发明实施例1、5至10不同表面活化剂处理随着反应的进行得到的InP量子点的第一激子峰示意图；
图3示出了采用UV-vis测试检测根据本发明实施例1、11至13、23和24不同In前体和配体得到的InP量子点的紫外吸收示意图；
图4示出了采用UV-vis测试检测根据本发明实施例1、14至19在不同温度下得到的InP量子点的紫外吸收示意图；
图5示出了采用UV-vis测试检测根据本发明实施例1、20至22不同表面活化剂浓度得到的InP量子点的紫外吸收示意图；
图6的(a)和(b)示出了采用UV-vis测试和荧光光谱仪检测根据本发明实施例13得到的不同尺寸的核壳量子点的紫外吸收光谱和荧光发射光谱示意图，图6的(d)分别是InP量子点，InAs量子点和InAs/InP量子点在有无表面活化剂存在下的紫外吸收光谱示意图；
图7示出了根据本申请对实施例2制备的晶种和实施例1反应20min得到量子点的透射电镜测试图和粒径尺寸分布示意图，其中，(a)为实施例2制备的晶种的透射电镜测试图，(b)为实施例1反应20min得到量子点的透射电镜测试图，(c)为实施例1反应20min得到量子点的粒径尺寸分布示意图；
图8示出了根据本申请对比例1得到InP量子点的透射电镜测试图；以及
图9示出了采用UV-vis测试含有乙酸和不含有乙酸对晶种合成尺寸的影响。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
以下制备方法如无特殊说明，均与现有技术中制备量子点对反应环境的要求相同，在反应之前均使用惰性气体气氛或其中除去湿气和氧气的空气气氛去除反应器中的湿气和氧气，其中的惰性气体为氮气、氩气或稀有气体。
如背景技术所记载的，现有技术中的量子点尺寸分布较宽，导致其性能受到影响，具体为如果生产出来的量子点群中的每个量子点尺寸不一样，则意味着光电转换性能不一样，那么这个量子点群应用范围受限，比如蓝光激发一个量子点产生红光一个量子点产生绿光，而应用效果较好的是蓝光激发每个量子点全部是产生一种光，光谱相同。
为了解决该问题，在本申请一种典型的实施方式中，提供了一种III-V族量子点的制备方法，该制备方法包括：S1，将III族元素前体、溶剂、表面活化剂、III-V族量子点晶种混合，得到混合体系；S2，加热混合体系至第一温度；以及S3，向温度为第一温度的混合体系中加入V族元素前体，得到III-V族量子点，其中，III-V族量子点晶种带有羧酸配体，表面活化剂为乙酰丙酮或乙酰丙酮的衍生物或带有羧酸基团的化合物RCOOH，第一温度为120℃～200℃之间，上述衍生物具有以下结构式：
Figure PCTCN2016104257-appb-000003
其中，P1和P2分别独立地选自烷基、具有取代基的烷基、烯基、具有取代基的烯基和芳基中的任意一种基团。
由于在加入V族元素前体之前III族元素前体、溶剂、表面活化剂和III-V族量子点晶种是没有发生化学反应的，因此，III族元素前体、溶剂、表面活化剂和III-V族量子点晶种的添加没有特定的顺序，为了更好地使物质相互接触，优选III族元素前体、溶剂与表面活化剂先混合，然后再向其中加入III-V族量子点晶种，得到该混合体系。
上述制备方法中，晶种提供了成核位点，在热扰动下，表面活化剂部分替换晶种表面的原有配体，因为原有配体与晶种表面的结合能力较强，会阻碍自由单体在晶种表面的结合，而表面活化剂与晶种表面的结合能力较弱，即表面活化剂具有快速与晶体表面结合和非结合状态的切换能力，使得自由的单体反应物在晶种上生长而不是自成核，因为自成核的能垒比在晶种上生长更高，因此可以使成核和生长分开，进而利于III-V族量子点纳米晶的生长。
加入V族元素前体后，III族元素和V族元素生长到晶种表面，表面活化剂对生长后的晶体表面进行蚀刻从而达到活化目的，促使更多的III族元素和V族元素继续生长到晶体表面，从而实现晶体的生长。表面活化剂为带有羧酸基团的化合物RCOOH时，当表面活化剂失去一个质子，III-V族量子点晶种的羧酸配体会得到质子，表面活化剂变成III-V族量子点纳米晶的配体，通过这种配体交换，表面羧酸配体和自由酸达到一个动态平衡，这种表面活化可避免III-V族量子点表面形成III族元素-O键，进而有利于在晶种表面的III-V族量子点纳米晶的生长，形成粒径分布均一的III-V族量子点。表面活化剂为乙酰丙酮及其衍生物时，在上述反应温度下，部分乙酰丙酮及其衍生物被转换成乙酰丙酮及其衍生物配体，完成和羧酸配体的交换，使得III-V族量子点晶种吸收发生蓝移，达到蚀刻III-V族量子点晶种的目的，并得到 双齿配位的III-V族量子点晶种，由于双齿配位具有较小的空间位阻，使得后续加入的V族元素前体能够有效地与体系里的III族前体反应，在晶种表面继续生长，并抑制了III族前体和V族前体的自成核现象，从而形成粒径分布均一的III-V族量子点。
同时，将上述反应温度控制在120℃以上，可以有效避免III族元素和V族元素不在晶种表面上生长而是独立生成核，而影响粒径分布。将上述反应温度控制在120～200℃之间，一方面有效避免III-V族量子点晶种被氧化，另一方面减少表面活化剂的挥发，节约原料使用量，且更为环保。
在本申请一种更为优选的实施例中，上述第一温度在140～180℃之间，更有利于对所得到的量子点粒径分布的控制。
优选，上述衍生物具有以下结构式：
Figure PCTCN2016104257-appb-000004
其中，m为0～4的整数，n为0～4的整数。
本申请利用上述制备方法所得到的III-V族量子点的粒径大小是可以通过V族元素前体的添加量进行控制的，优选上述S3包括将V族元素前体分批添加入混合体系中，并根据III-V族量子点的紫外第一激子峰，来确定补加的用量和次数。
在本申请一种优选的实施例中，表面活化剂为RCOOH，其中R是碳数≤6饱和烃基，优选RCOOH为乙酸、丙酸或异丙酸。上述烷基酸由于碳链长度适中，空间位阻小，因此能够和晶种的配体更快地交换。
本申请的III族元素前体可以为A(B)2C、A(C)3或A(D)3的任意一种，其中，A为III族元素，B为脂肪酸根，C为碳数≤6的脂肪酸根或CH3COCH2COCH2-，D为卤素离子，V族前体可以为(三甲基硅基)磷(TMS3P)、三(三乙基硅基)磷(TES3P)和三(三甲基硅基)砷(TMS3As)中的任意一种，所述步骤S1中的溶剂可以是非配位溶剂，比如长链脂肪烷烃或者长链脂肪烯烃的，优选十四烷烃或十八烯烃。
本申请中表面活化剂主要是为了提供与III-V族量子点晶种的羧酸配体进行交换的基团，为了实现两者交换后形成稳定的动态平衡体系，优选表面活化剂在混合体系的浓度为0.025～0.125mol/L。浓度低于0.025mol/L，蚀刻作用很小，但浓度增加至0.125mol/L后如果继续增加，并没有带来明显生长速度的提高。当然浓度更高也是可以反应，由于没有带来生长速度的明显提高，因此从节约原料提高效率的角度来讲，将最高浓度控制在0.125mol/L。此外，由于本申请在120℃以上反应，因此，一些低沸点的表面活化剂可能会有一定程度的挥发，为了保证在全程反应中具有足够的表面活化剂，可以适当增加表面活化剂的浓度。
在合成III-V族量子点晶种的过程中，优选的配体为18≥碳数≥8的羧酸盐配体，例如辛酸盐、癸酸盐、十四酸盐、硬脂酸盐或油酸盐。由于羧酸配体碳链较长时空间位阻较大，由于其空间位阻大，因此置换下来的羧酸会阻碍量子点的继续生长，从而无法合成大尺寸的量子点。当在体系中加入表面活化剂时，由于可以先就III-V族晶种的表面羧酸配体进行配体交换，进而活化晶种的表面，促使后续加入的V族前体能够均匀地生长在晶种的表面，因此能够很好地实现均一III-V族量子点的合成。
本申请所采用的III-V族量子点晶种可以利用现有技术合成晶种的方法来制作。优选的，晶种合成法基于烷胺法，烷胺作为配体，该法能够提高III族前体的反应活性，降低反应温度，从而抑制晶种表面的氧化铟生成，有利于后续单体反应物在晶种表面的生长。发明人通过实验发现在晶种合成时，当In前体是通过In(Ac)3和肉豆蔻酸反应生成InMy2Ac时，该反应还生成了乙酸，对反应后的产物体系鼓氩气20min除去乙酸后加P前体，晶种尺寸合成比较小，而不除去乙酸时，晶种尺寸合成比较大。当In前体是直接准备好的InMy2Ac时，即不存在乙酸时，晶种尺寸合成比较小。结果比较见图9，波长红移说明尺寸越大。这也证明了乙酸具有表面活化作用。
在本申请另一种典型的实施方式中，还提供了一种III-V族量子点，该III-V族量子点的粒径分布的相对标准偏差(relative standard deviation,RSD)≤10％。由于量子点的粒径分布较窄，荧光发射光谱的半峰宽依然能够维持在40nm左右，半峰宽越窄，则峰型越尖，颜色越纯粹。该III-V族量子点可以采用上述制备方法制备而成。
在得到上述III-V族量子点后，可以对其进行加壳处理，得到核壳纳米晶。因此，在本申请又一种典型的实施方式中，还提供了一种核壳纳米晶，该核壳纳米晶包括核和壳层，其中，核为上述的III-V族量子点，壳层包括IIB-VI族元素或III-V族元素。可以利用现有技术进行加壳处理。
本申请制备的III-V族量子点因为半峰宽窄、均一性高，所以光电性能优秀。可以用于量子点组合物，适用于诸如生物检测、太阳能、显示、照明等；可以用于量子点膜作为光转换器件，提高显示器的色域，还可以用来作为电致发光器件中的发光物质，替代有机电致发光器件的有机发光物质。
以下将结合实施例和对比例，进一步说明本申请的有益效果。
所涉及的化学物质的说明
醋酸铟(In(Ac)3)，99.99％金属铟的乙酰丙酮(In(acac)3，98％)，碱式碳酸锌(Zn5(CO3)2(OH)6，97％，Zn＞57％)，己酸(HHe，98％)、辛酸(98％)、癸酸(HDe，99％)，肉豆蔻酸(HMy，98％)，硬脂酸(HSt，90％)、油酸(HOl，90％)，辛胺(98％)，硒粉(200目、99.999％)，1-十八烯(ODE，90％)、正十四烷(99％)，三辛基膦(TOP，90％)乙酰丙酮(Hacac，99+％)，2,4-壬二酮(99+％)，乙酸(Hac、99±％)。三(三甲基硅基)膦(TMS3P，在己烷中，10wt％，>98％)、三(三乙基硅基)膦(TES3P，在己 烷中，10wt％，>98％)、三(三甲基硅基)砷(TMS3As，在己烷中，10wt％，>98％)是由纳晶科技股份有限公司自主合成。TMS3P、TES3P、TMS3As使用前蒸馏并存放在手套箱。
实施例1 InP量子点的合成
III族元素前体的制备
InMy2Ac的合成：
5mmol In(Ac)3和17.5mmol HMy混合Ar气保护下加热到140℃保持6小时，得到产物，将产物用丙酮洗涤3次以除去多余的HMy，真空干燥过夜，得到InMy2Ac。
InDe2Ac和InSt2Ac的合成：
方法同InMy2Ac的合成，除了用HDe或HSt替换掉HMy。
InMy2acac的合成
方法同InMy2Ac，除了用In(acac)3替换掉In(Ac)3。
My-配体500nm III-V族量子点晶种的制备
My-配体InP晶种的合成：
0.15mmol In(acac)3，0.45mmol HMy和3.5ml ODE混合于25ml烧瓶中，Ar鼓泡10min，然后搅拌下升温至185℃，得到In前体；向In前体中注入0.075mmol TMS3P、0.75mmol辛胺和ODE(共0.8ml)混合液(即第二P前体)，进行晶种生长，生长温度设置为178℃。采用UV-vis测试检测，当第一激子峰在500nm左右时即表明粒子长大到所需的大小，撤去加热套，得到含有带有My-配体的InP晶种的产物体系。
InP晶种的原位纯化:
4ml己烷和8ml甲醇加入50℃的含有带有羧酸配体的InP晶种溶液中搅拌2.5min。静置，分层后用针筒将下层无色溶液分离保留上层己烷/ODE相。然后，70℃下将己烷/ODE相用Ar气鼓泡，得到带有My-配体的InP晶种。注意：己烷和甲醇使用前用Ar鼓泡除氧，然后放入分子筛存储。
De-或St配体的500nm InP晶种的合成：合成方法同My-配体InP晶种，只是用HDe或HSt替换掉HMy。
InP量子点的合成:
0.15mmol的InMy2Ac和2.5ml十四烷形成的混合液放置于25ml烧瓶中。利用Ar气向混合液鼓泡10min后，将0.3mmol Hacac注入到混合液中得到初始混合体系，并将初始混合体系加热至160℃，得到初始热混合体系。向初始热混合体系中加入2×10-7mol的带有My-配体的InP晶种(约1.5ml)得到混合体系(表面活化剂Hacac在混合体系的浓度为0.075mol/L)，将该混合体系升温至160℃，得到热混合体系。向热混合体系中以0.05ml/min速度注入0.05 mmol TMS3P和0.5ml ODE的混合液，160℃下保持反应20min，同时采用UV-vis测试检测不同反应时间得到的InP量子点的发射峰，具体检测结果见图1和图2。根据需要滴加多次TMS3P，当紫外吸收峰达到目标波长后，可停止滴加，对应不同波长的InP量子点谱图见图6(a)。量子点表面配体交换前后的配体密度见表1。
实施例2 InP/ZnSe核壳量子点的合成
油酸锌(Zn(Ol)2)的合成：
1mmol Zn5(CO3)2(OH)6和11mmol HOl混合于烧瓶中，Ar气氛中加热至200℃形成澄清溶液，然后保持搅拌1小时。1小时后溶液降温至室温，用丙酮沉淀。得到的沉淀用丙酮清洗三次，并真空干燥过夜。
Se前体的制备：
0.2mM TOPSe溶液的制备：2mmol Se粉和5mmol TOP然后手套箱中加入6.13g ODE混合。
实施例1得到的含有不同波长的InP量子点的体系降温至150℃，0.2mmol辛酸注入该体系中，5min后，向该体系中加入一定量的油酸锌ODE溶液(0.2mM)，温度升至260℃，然后加入于油酸锌等量的TOPSe溶液，保持反应30min。同时采用PL光谱测试检测反应30min后得到的InP/ZnSe量子点的荧光发射光谱，具体检测结果见图6(b)。
实施例3 InAs量子点的合成
My-配体650nm的InAs晶种的合成：
0.15mmol In(Ac)3、0.45mmol HMy和3.5ml ODE放置于25ml烧瓶中，150℃下Ar气鼓泡30min得到In前体；将In前体温度升到240℃，注入0.01875mmol TMS3As的ODE溶液(0.8ml)，反应温度设为230℃进行反应。采用UV-vis测试检测，当第一激子峰在650nm左右时即表明粒子长大到所需的大小，撤去加热套，得到含有带有My-配体的InP晶种的产物体系。
InAs晶种的原位提纯：过程同实施例2的提纯，除了第一次的时候在加入甲醇后加入0.15ml的油胺。第二次，只加入己烷和甲醇。
InAs量子点的合成：
0.15mol InDe2Ac和2.5ml十四烷加入25ml形成的混合液置于烧瓶中，利用Ar气向混合液鼓泡10min后，向混合液中注入0.3mmol HAc得到初始混合体系，并将初始混合体系加热至160℃，得到初始热混合体系。向初始热混合体系中注入2×10-7mol纯化后的带有My-配体的InAs晶种(约1.0ml)，得到混合体系(表面活化剂HAc在混合体系的浓度为0.075mol/L)，将该混合体系升温至160℃后得到热混合体系。向热混合体系中以0.025ml/min的速度滴加0.015mmol TMS3As的ODE溶液(1.0ml ODE)到反应液中，反应20min。同时采用UV-vis测试检测反应20min后得到的InAs量子点的吸收峰，具体检测结果见图6(d)。
实施例4 InAs/InP核壳量子点的合成
0.15mol InDe2Ac和2.5ml十四烷加入25ml形成的混合液置于烧瓶中。利用Ar气向混合液鼓泡10min后，向混合液中注入0.3mmol HAc得到初始混合体系，并将初始混合体系加热至160℃，得到初始热混合体系。向初始热混合体系中注入2×10-7mol实施例3纯化后的带有My-配体的InAs晶种(约1.0ml)，得到混合体系(表面活化剂HAc在混合体系的浓度为0.075mol/L)，将该混合体系升温至160℃后得到热混合体系。向热混合体系中以0.05ml/min的速度滴加0.05mmol的TMS3P的ODE溶液(1.0ml ODE)，保持20min生长InP壳。同时采用UV-vis测试检测反应20min后得到的InAs/InP核壳量子点的吸收峰，具体检测结果见图6(d)。
实施例5至10表面活化剂不同时，InP量子点的合成
合成方法同实施例1，只是用HAc,HHe,HDe,HMy和HSt，2,4-壬二酮依次替换掉Hacac。同时采用UV-vis测试检测反应20min后得到的InP量子点的发射峰，具体检测结果见图1，采用UV-vis测试检测不同反应时间得到的InP量子点的发射峰，具体检测结果见图2，其中2,4-壬二酮和Hacac的结果重合。
实施例11至13不同In前体的Hacac活化的InP量子点的合成
合成方法同实施例1，只是将InMy2Ac前体依次替换成InDe2Ac、InSt2Ac和InMy2acac。同时采用UV-vis测试检测反应20min后得到的InP量子点的发射峰，具体检测结果见图3。
实施例14至19不同反应温度
合成方法同实施例1，反应温度依次为120℃、140℃、180℃、200℃同时采用UV-vis测试检测反应20min得到的InP量子点的发射峰，具体检测结果见图4。
实施例20至22不同浓度的表面活化剂
合成方法同实施例1，表面活化剂Hacac在混合体系中的浓度依次为0.025mol/L、0.075mol/L、0.125mol/L，同时采用UV-vis测试检测反应20min得到的InP量子点的发射峰，具体检测结果见图5。
实施例23至24不同羧酸配体的晶种
合成方法同实施例1，但是晶种依次替换为De-配体的500nm InP晶种、St-配体的500nm InP晶种，同时采用UV-vis测试检测反应20min得到的InP量子点的发射峰，具体检测结果见图3。
对比例1
与实施例1相同的方法，但不加晶种表面活化剂，得到对比例1的量子点。
对上述实施例2的晶种和实施例3反应20min得到InP量子点采用X射线衍射法(XRD)测量其尺寸，其中仪器为理学Ultimate-IV X射线衍射仪，测试条件40kV/40mA使用Cu Kα线
Figure PCTCN2016104257-appb-000005
量子点用丙酮沉淀离心后置于玻璃基板测试。测试结果见图7。
对实施例2制备的晶种和实施例1和对比例1反应20min得到量子点采用透射电镜进行检测，检测结果见图7和图8。
表1
量子点 C％ H％ N％ NMy-(nm-2) N胺(nm-2) Nacac-(nm-2)
初始晶种 43.16 7.05 0.2 6.9 0.4 0
经Hacac活化后的量子点 34.86 5.35 0 4.1 0 1.6
由表1可以看出，经过配体交换后，量子点表面配体的种类及每平方纳米的配体个数发生了变化，C、H、N元素的质量分数也证明了这一现象。
由图1可以看出，采用本申请的方法后，晶种明显长大，且在相同的反应条件下，当表面活化剂为RCOOH时，R的碳数≤6时，所得到的量子点粒径尺寸较大，R的碳数>6时，尺寸增加，而当表面活化剂为乙酰丙酮时，量子点粒径尺寸相对较大，说明RCOOH具有表面活化作用。
由图2可以看出，随着反应时间的增加，晶种逐渐长大，至反应时间延长至20min时，量子点的粒径尺寸趋于恒定，没有明显增加。
由图3可以看出，在带有不同长链脂肪酸配体的InP晶种的存在下，以不同的脂肪酸盐作为III族前体，以乙酸或者乙酰丙酮作表面活化剂，从其紫外吸收光谱的变化表明，都能制备得到相应尺寸的InP量子点。
由图4可以看出，反应温度为120℃时，晶种即刻增长；但是当反应温度继续增加时晶种的增长并不明显，且在140℃、160℃、180℃、200℃四个温度下，分别等量加入III族前体，紫外吸收峰没有发生红移，说明最终的量子点尺寸是一样的，生长速度是一样的，因此说明温度升高至140℃以上时，对生长速度和最终尺寸没有影响。
由图5可以看出，当表面活化剂的浓度为0.025mol/L时，可以发现晶种的生长，但是，当浓度上升至0.075mol/L后，浓度的继续上升并没有带来尺寸的提高。
由图6可以看出，(a)显示为紫外第一激子峰500～650nm的InP量子点的紫外吸收光谱，(b)显示发射峰500～700nm的InP/ZnSe量子点的荧光发射(PL)光谱，(d)显示为InAs在有无表面活化剂的情况下生长InAs和InP的紫外吸收光谱图。
由图7可以看出，(a)是InP晶种的透射电镜图，其尺寸大小为1.97nm，RSD大约为14.5％，(b)显示InP晶种生长完的透射电镜图，其尺寸大小为3.84nm，RSD大约为6.7％，(c)显示所得到量子点晶体结构为闪锌矿结构，(d)显示粒径尺寸的标准偏差为6.7％，达到一般的II-VI族量子点水平，说明本申请得到的III-V族量子点的粒径分布较窄。
由图8可以看出，对比例1得到的量子点形状是不均一的，并且继续加V族元素前体量子点不生长。
由图9可以看出，HAc的存在能使晶种尺寸更大，说明HAc具有表面活化剂作用。
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
上述制备方法中，晶种提供了成核位点，在热扰动下，表面活化剂部分替换晶种表面的原有配体，因为原有羧酸配体与晶种表面的结合能力较强，会阻碍自由单体在晶种表面的结合，而表面活化剂与晶种表面的结合能力较弱，即表面活化剂具有快速结合和非结合状态的切换能力，使得自由的单体反应物可以在晶种上生长而不是自成核，因为自成核的能垒比在晶种上生长更高，因此可以使成核和生长阶段分开，进而利于III-V族量子点纳米晶的生长。
加入V族元素前体后，III族元素和V族元素生长到晶种表面，表面活化剂对生长后的晶体表面进行蚀刻从而达到活化目的，促使更多的III族元素和V族元素继续生长到晶体表面，从而实现晶体的生长。表面活化剂为带有羧酸基团的化合物RCOOH时，当表面活化剂失去一个质子，III-V族量子点晶种的羧酸配体会得到质子，表面活化剂变成III-V族量子点纳米晶的配体，通过这种配体交换，表面羧酸配体和自由酸达到一个动态平衡，这种表面活化可避免III-V族量子点表面形成III族元素-O键，进而有利于在晶种表面的III-V族量子点纳米晶的生长，形成粒径分布均一的III-V族量子点。表面活化剂为乙酰丙酮及其衍生物时，在上述反应温度下，部分乙酰丙酮及其衍生物被转换成乙酰丙酮及其衍生物化物配体，完成和羧酸配体的交换，使得III-V族量子点晶种吸收发生蓝移，达到蚀刻III-V族量子点晶种的目的，并得到双齿配位的III-V族量子点晶种，由于双齿配位具有较小的空间位阻，使得后续加入的V族元素前体能够有效地与体系里的III族前体反应，在晶种表面继续生长，并抑制了III族前体和V族前体的自成核现象，从而形成粒径分布均一的III-V族量子点。
同时，将上述反应温度控制在120～200℃之间，一方面有效避免III-V族量子点晶种被氧化，另一方面减少表面活化剂的挥发，节约原料使用量，且更为环保。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (13)

  1. 一种III-V族量子点的制备方法，其特征在于，所述制备方法包括：
    S1，将III族元素前体、溶剂、表面活化剂、III-V族量子点晶种混合，得到混合体系；
    S2，加热所述混合体系至第一温度；以及
    S3，向温度为所述第一温度的所述混合体系中加入V族元素前体，得到所述III-V族量子点，
    其中，所述III-V族量子点晶种带有羧酸配体，所述表面活化剂为乙酰丙酮或乙酰丙酮的衍生物或带有羧酸基团的化合物RCOOH，所述第一温度为120℃～200℃之间，所述衍生物具有以下结构式：
    Figure PCTCN2016104257-appb-100001
    其中，P1和P2分别独立地选自烷基、具有取代基的烷基、烯基、具有取代基的烯基和芳基中的任意一种基团。
  2. 根据权利要求1所述的制备方法，其特征在于，所述第一温度在140～180℃之间。
  3. 根据权利要求1所述的制备方法，其特征在于，所述衍生物具有以下结构式：
    Figure PCTCN2016104257-appb-100002
    其中，m为0～4的整数，n为0～4的整数。
  4. 根据权利要求1所述的制备方法，其特征在于，所述RCOOH中的R是碳数≤6饱和烃基，优选所述RCOOH为乙酸、丙酸或异丙酸。
  5. 根据权利要求1所述的制备方法，其特征在于，所述表面活化剂在所述混合体系的浓度为0.025～0.125mol/L。
  6. 根据权利要求1所述的制备方法，其特征在于，所述步骤S3包括将所述V族元素前体分批加入所述混合体系中。
  7. 根据权利要求1所述的制备方法，其特征在于，所述III族元素前体为A(B)2C、A(C)3或A(D)3，其中，A为III族元素，B为碳数≥8的脂肪酸根，C为碳数≤6的脂肪酸根或CH3COCH2COCH2-，D为卤素离子。
  8. 根据权利要求1所述的制备方法，其特征在于，所述羧酸配体为碳数≥8的羧酸盐配体，
    优选辛酸盐、癸酸盐、十四酸盐、硬脂酸盐或油酸盐。
  9. 一种III-V族量子点，其特征在于，所述III-V族量子点的粒径分布的相对标准偏差≤10％。
  10. 一种核壳纳米晶，包括核和壳层，其特征在于，所述核为权利要求1至8中任一项所述的制备方法制备而成的III-V族量子点或权利要求9所述的III-V族量子点，所述壳层包括IIB-VI族元素或III-V族元素。
  11. 一种组合物，包括III-V族量子点，其特征在于，所述III-V族量子点为权利要求1至8中任一项所述的制备方法制备而成的III-V族量子点或权利要求9所述的III-V族量子点。
  12. 一种量子点膜，包括III-V族量子点，其特征在于，所述III-V族量子点为权利要求1至8中任一项所述的制备方法制备而成的III-V族量子点或权利要求9所述的III-V族量子点。
  13. 一种电致发光器件，包括发光物质，其特征在于，所述发光物质包括III-V族量子点，所述III-V族量子点为权利要求1至8中任一项所述的制备方法制备而成的III-V族量子点或权利要求9所述的III-V族量子点。
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