WO2022143343A1 - 一种量子点分散液及量子点保存方法 - Google Patents

一种量子点分散液及量子点保存方法 Download PDF

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WO2022143343A1
WO2022143343A1 PCT/CN2021/140506 CN2021140506W WO2022143343A1 WO 2022143343 A1 WO2022143343 A1 WO 2022143343A1 CN 2021140506 W CN2021140506 W CN 2021140506W WO 2022143343 A1 WO2022143343 A1 WO 2022143343A1
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quantum dot
quantum dots
quantum
dispersion liquid
dot dispersion
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French (fr)
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周礼宽
杨一行
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Tcl科技集团股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium

Definitions

  • the present disclosure relates to the technical field of quantum dots, and in particular, to a quantum dot dispersion liquid and a quantum dot storage method.
  • Quantum dots generally consist of inorganic nanocrystals and surface ligands formed on the surfaces of the inorganic nanocrystals, wherein the inorganic nanocrystals may be core-shell structured inorganic nanocrystals.
  • the core-shell structure inorganic nanocrystal specifically includes a quantum dot crystal core and a multi-shell layer structure covering the quantum dot crystal core.
  • the crystal cores of the quantum dots are connected with the surface ligands through the multi-shell layer, so that a quantum dot light-emitting material with high fluorescence quantum efficiency and good stability can be obtained.
  • the synthesized quantum dots need to be preserved. Specifically, after the synthesized quantum dots are purified, they are dispersed into an organic phase, an alcohol phase or an aqueous phase solvent for low temperature preservation. However, the problem of fast or slow fluorescence quantum yield decay occurs during the storage process of quantum dot luminescent materials.
  • the purpose of the present disclosure is to provide a quantum dot dispersion liquid and a quantum dot storage method, aiming at solving the problem that the quantum dot luminescent material will decay in fluorescence quantum yield during storage.
  • a quantum dot dispersion liquid comprising: a dispersant, quantum dots and reducing organic matter.
  • the quantum dot dispersion wherein the reducing organic matter is selected from one or more of alcohols, phenols, aldehydes, organic amines, organic phosphorus, and olefins;
  • the reducing organic matter is selected from one or more of ethanolamine, tributylphosphine, and polyethylene glycol amine.
  • the quantum dots are quantum dots containing surface ligands.
  • the surface ligands include one or more of carboxyl surface ligands, amine-based surface ligands, thiol surface ligands and phosphine-based surface ligands.
  • the reducing organic matter is a reducing organic matter containing a coordinating group.
  • the coordinating group includes at least one of a carboxyl group, an amine group, a mercapto group, and a phosphine group.
  • the coordination activity of the coordinating group and the quantum dot is stronger than the coordination activity of the surface ligand and the quantum dot.
  • the quantum dot dispersion liquid wherein, the dispersing agent comprises chloroform, toluene, n-hexane, cyclohexane, n-heptane, decane, n-octane, cycloheptane, dioxane, water, methanol, One or more of ethanol, isopropanol, n-butanol;
  • the molar ratio of the reducing organic matter to the quantum dots is 0.5:1 to 2:1;
  • the concentration of the quantum dots is 1 mmol/mL ⁇ 100 mmol/mL;
  • the quantum dots are selected from one or more of group II-VI compound quantum dots, group IV-VI compound quantum dots, group III-V compound quantum dots, and group I-VI compound quantum dots.
  • the quantum dots are core-shell quantum dots formed by coating the quantum dot crystal core with a single-layer or multi-layer semiconductor material shell layer.
  • the quantum dot dispersion liquid wherein, the quantum dot crystal nucleus is selected from CdSe, CdS, CdTe, CdSeTe, CdZnS, PbSe, ZnTe, CdSeS, PbS, PbTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, At least one of InP, InAs, InZnP, InGaP, InGaN, CdZnSe, and CdZnSe.
  • the shell layer of the semiconductor material is selected from at least one of ZnSe, ZnS and ZnSeS.
  • the quantum dots are red quantum dots CdZnSe/ZnSe/ZnS or green quantum dots CdZnSe/ZnS.
  • a quantum dot preservation method comprising:
  • the quantum dots, the reducing organic substance, and the dispersing agent are prepared into the quantum dot dispersion liquid according to any one of claims 1 to 8, and the quantum dots are stored.
  • the storage method for quantum dots wherein the storage temperature is 20-30°C.
  • the quantum dot dispersion described in the present disclosure contains reducing organic matter, which can eliminate and resist oxidation reaction factors generated by factors such as dispersing agent and water, oxygen, and light in the air, thereby effectively ensuring that quantum dots are in
  • the fluorescence stability during the storage process solves the problem of the reduction of the fluorescence quantum yield caused by the influence of water, oxygen, light and other factors during the storage process of the quantum dots.
  • the present disclosure provides a quantum dot dispersion liquid and a quantum dot storage method.
  • a quantum dot dispersion liquid and a quantum dot storage method.
  • the synthesized quantum dots are separated from the reaction system containing the reaction solvent, unconverted precursors and excess organic ligands to obtain quantum dots composed of inorganic nanocrystals and organic surface ligands,
  • the obtained quantum dots are dispersed in a solvent for preservation.
  • the inventors found in their work on quantum dot luminescent materials that storage conditions such as temperature, illumination, and water-oxygen environment have important effects on the optical properties and stability of quantum dots.
  • the quantum dot inorganic nanocrystals are dispersed in different solvents, and the solvent can be an organic phase, an alcohol phase or an aqueous phase solvent. Since the surface ligands and the core-shell structure of the quantum dots are connected by coordination bonds, in the dispersant, the surface ligands are easily detached from the surface of the inorganic nanocrystals of the core-shell structure of the quantum dots, resulting in the formation of defects on the surface of the quantum dots. When an electron or hole is captured, it can act as an active center for a redox reaction that reacts with water and oxygen in the air, thereby destabilizing the quantum dot's fluorescence.
  • the surface of the quantum dots adsorbs water molecules from the solvent or air environment, which oxidizes the metal atoms on the surface of the inorganic nanocrystals of the quantum dots, resulting in defects and a decrease in the fluorescence quantum efficiency.
  • quantum dots are purified and stored in organic phase, alcohol phase or aqueous phase solvent. Under the influence of environmental temperature, light, water and oxygen and other storage conditions, reactions such as oxidation will occur, interfering with mobile electrons and holes. , resulting in irreversible photoquenching. Among them, the water molecules adsorbed on the surface of the quantum dots will oxidize the surface of the quantum dots, resulting in a blue-shift of exciton emission, and finally introducing new surface defects, reducing the luminescence intensity of the quantum dots. The photo-oxidation of quantum dots will generate new defects to suppress the emission of excitons, resulting in lower luminescence quantum yields (luminescence QY).
  • the wide bandgap shell In addition to the surface ligands connected by coordination bonds in the outer layer of the quantum dot core, the wide bandgap shell also maintains the fluorescence quantum yield. However, in the wet oxygen environment, the surface of the quantum dot is freed by the oxygen formed on the surface of the wide bandgap shell. The effect of the radical anion adsorbate, resulting in a reduced degree of electron wavefunction confinement. In addition, oxygen has a certain permeability in the non-smooth energy level gradient between the core and shell of quantum dots. Even for quantum dots with thick shells, oxygen molecules can reach the core of quantum dots through the core-shell interface, resulting in defect vacancies and reduced fluorescence quantum yield. Rate.
  • the decay of the fluorescence quantum yield caused by the damage to the quantum dot structure caused by the factors of temperature, light, water and oxygen is directly related to the externally generated oxidation factor.
  • the reducing organic matter method eliminates the oxidation factors generated by environmental factors such as temperature or light, water and oxygen, and avoids the irreversible damage to the surface or interior of the quantum dot caused by the negatively charged oxygen radicals caused by these oxidation factors, resulting in a decrease in the fluorescence quantum yield. , affecting the optoelectronic properties of quantum dots.
  • Embodiments of the present disclosure provide a quantum dot dispersion, which includes: a dispersant, quantum dots, and reducing organic matter.
  • the reducing organic matter can eliminate and resist the oxidation reaction factors generated by the dispersing agent and factors such as water, oxygen, light in the air, etc., thereby effectively ensuring the long-term preservation of quantum dots It can effectively solve the problem of reducing the fluorescence quantum yield caused by the influence of water, oxygen, light and other factors during the storage process of quantum dots.
  • the reducing organic compound is an organic compound with weak reducibility, and the reducing organic compound is selected from one of alcohols, phenols, aldehydes, organic amines, organic phosphorus, and alkenes. one or more.
  • the reducing organics in this embodiment are not limited to the above-mentioned types of reducing organics, for example, the reducing organics may also be other compounds containing double bonds.
  • the reducing organic matter that can be dispersed in the corresponding dispersing agent can be selected according to different dispersing agents.
  • the quantum dots are quantum dots containing surface ligands
  • the quantum dots include inorganic nanocrystals
  • the quantum dots are bound on the surface of the inorganic nanocrystals.
  • organic ligands include one or more of carboxyl surface ligands, amine surface ligands, sulfhydryl surface ligands and phosphine surface ligands.
  • the surface ligands include one or more of short-chain or long-chain organics containing carboxyl groups, amine groups, sulfhydryl groups and phosphine groups, and the surface ligands are linked with the inorganic nanocrystal surface cations in the form of coordination bonds.
  • the surface ligand may be 9-carboxy-2-octylpyrene, trioctylphosphine, octadecylamine, octadecylthiol, and the like.
  • the shedding of the surface ligands of the quantum dots is also one of the main reasons for the surface defects of the quantum dots.
  • the detachment of the surface ligands of the quantum dots will produce a certain quenching effect on the excitons delocalized to the surface, resulting in a low fluorescence quantum yield.
  • surface dangling bonds generated by lattice defects can affect the optical properties of quantum dots.
  • the surface properties of quantum dot inorganic nanocrystals have little effect on the quantum dots in the ground state, but have a huge impact on the performance of quantum dots in the excited state.
  • the existence of defects on the surface of quantum dots will introduce defect state energy levels.
  • the defect energy level When the defect energy level is higher than the excitons When the energy level is low, the defect energy level may trap electrons and holes, and then the excitons recombine through the defect state, and the energy is released in the form of light or heat.
  • the defect energy level By coating the surface of quantum dots with surface ligands, lattice defects are eliminated, so that quantum dots have better fluorescence stability. Generally speaking, surface ligands with longer chains and greater steric hindrance are selected. .
  • the reducing organic substance is a reducing organic substance containing a coordinating group
  • the reducing organic substance containing a coordinating group means that the molecular chain of the reducing organic substance is connected with ligands.
  • the coordinating group can form a coordinate bond with the surface cations of the inorganic nanocrystal.
  • the surface ligands include one or more of carboxyl surface ligands, amine surface ligands, sulfhydryl surface ligands and phosphine surface ligands, that is, the coordinating group includes carboxyl groups , at least one of amine group, mercapto group and phosphine group.
  • the carboxyl, amine, sulfhydryl, phosphine and other coordinating groups in the reducing organics described in this example can complement the lattice defects on the surface of the quantum dots due to the shedding of organic ligands, so as to avoid the resulting defect quenching Exciton out, reducing the problem of fluorescence quantum yield.
  • the coordination activity of the coordinating group and the quantum dot is stronger than the coordination activity of the surface ligand and the quantum dot. That is, the coordination activity of the selected reducing organics is stronger than that of the surface ligands, wherein the coordination activity refers to the ease with which the coordination group or the surface ligands form coordination bonds with the inorganic nanocrystals. degree or the degree of stability of the formation of coordination bonds. In the embodiments of the present disclosure, more stable coordination bonds can be formed on the surface of the inorganic nanocrystal by selecting a reducing organic compound with higher coordination activity than the surface ligand.
  • the order of coordination activity of the coordinating group is mercapto>amine>carboxyl>phosphine group, while for the same coordinating group, the order of coordination activity is short chain>long chain (with the reducibility of the coordinating group The longer the organic molecular chain, the lower the coordination activity of reducing organics containing coordinating groups).
  • a reducing organic compound with higher coordination activity than the surface ligand is selected according to the above-mentioned order of the activity of the coordinating group.
  • the reducing organic compound is selected from one or more of ethanolamine, tributylphosphine, and polyethylene glycol amine.
  • the ethanolamine, tributylphosphine and polyethylene glycol amine have reducibility and can eliminate the oxidation factors caused by environmental factors such as temperature or light, water and oxygen; at the same time, they also contain coordinating groups such as amine group and phosphine group respectively,
  • the vacancy defects on the surface of the quantum dots due to ligand shedding can be complemented to avoid the reduction of the fluorescence quantum yield.
  • the reducing organic matter to be added can be selected to meet the requirement that it can be dispersed in an organic phase, an alcohol phase or an aqueous phase solvent.
  • the reducing organic matter with good solubility in the dispersant By selecting the reducing organic matter with good solubility in the dispersant, a uniform and stable quantum dot dispersion is formed, so that the reducing organic matter can move freely in the dispersion liquid, which is beneficial to realize the reducing organic matter as the surface through free movement
  • the morphology of the ligands forms bonds with the surface of the quantum dot inorganic nanocrystals, thereby filling the defects caused by the exfoliation of the ligands on the surface in situ.
  • reducing organic compounds can be selected based on similar compatibility principles, for example, polar reducing organic compounds are selected for polar dispersants, and non-polar reducing organic compounds are selected for non-polar dispersing agents.
  • the dispersant described in this example is used to disperse quantum dots and reducing organic matter.
  • the quantum dot dispersant includes an organic phase solvent, an alcohol phase solvent or an aqueous phase solvent.
  • the organic phase solvent can be one or more of chloroform, toluene, n-hexane, cyclohexane, n-heptane, decane, n-octane, cycloheptane and dioxane;
  • the alcoholic phase solvent can be methanol, One or more of ethanol, isopropanol, n-butanol, etc.;
  • the aqueous phase solvent is deionized water.
  • the dispersing agent in this embodiment can be a non-polar solvent, such as dichloroethane, or a polar solvent, such as water.
  • the molar ratio is less than 0.5: At 1, the amount of reducing organic matter added is relatively small, and the effect of eliminating the oxidation factor in the dispersant and supplementing the surface ligands of the quantum dots is poor.
  • the measured fluorescence quantum yield data it will still be significantly attenuated;
  • the molar ratio is greater than 2:1, the addition of too much reducing organic matter will affect the form of the quantum dots in the dispersant, and may form an organic coating layer on the surface of the quantum dots, affecting the application of the quantum dots.
  • the molar ratio of the reducing organic matter to the quantum dots in this embodiment is 0.5:1 to 2:1, so that there is a certain degree of reducing environment on the surface of the quantum dots, so as to avoid the fluorescence performance of the quantum dots being affected by the temperature in the environment, At the same time, the presence of a certain proportion of surface ligands in the dispersant can form dynamic complementation defects with the organic ligands that fall off the surface of the quantum dots, reducing the effect of surface defects. Fluorescence instability issues.
  • the quantum dots are selected from the group II-VI compound quantum dots, the IV-VI group compound quantum dots, the III-V group compound quantum dots, the I-VI group compound quantum dots, that is, the quantum dots are selected from II- At least one of single-structure quantum dots and composite-structure quantum dots of dot VI, IV-VI, III-V, and I-VI compounds.
  • the quantum dots are core-shell quantum dots.
  • the core-shell quantum dot is a composite structure quantum dot, specifically by using a single-layer or multi-layer semiconductor material shell layer to coat the quantum dot crystal core, for example, the quantum dot crystal core is selected from CdSe, CdS, CdTe, CdSeTe, At least one of CdZnS, PbSe, ZnTe, CdSeS, PbS, PbTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, InZnP, InGaP, InGaN, CdZnSe and CdZnSe; the semiconductor material shell is selected from ZnSe At least one of , ZnS and ZnSeS, the quantum dots can be red quantum dots CdZnSe/ZnSe/ZnS or green quantum dots CdZnSe/ZnS.
  • the lattice mismatch between the quantum dot core and the shell layer of the semiconductor material and the adjustment of the energy band deviation improve the performance of quantum dots.
  • the small lattice mismatch between the core and shell is conducive to the formation of alloy transition at the layer-core-shell interface. Reduce the interface defects caused by lattice stress to form non-radiative recombination centers; on the other hand, the large energy band deviation between the core and the shell is conducive to the binding of electron and hole wave functions in the core, away from the non-radiative recombination centers of the shell surface states, Therefore, the fluorescence stability and optoelectronic properties of quantum dots can be improved by the growth of multi-shell layers.
  • the concentration of the quantum dots is 1 mmol/mL to 100 mmol/mL, and the concentration of the quantum dots is 5 mmol/mL, 40 mmol/mL, 80 mmol/mL Wait.
  • Embodiments of the present disclosure provide a method for storing quantum dots, including:
  • the quantum dots, reducing organic matter, and dispersing agent are prepared into the quantum dot dispersion liquid as described above, and the quantum dots are stored.
  • the quantum dot preservation method described in this embodiment is to disperse the quantum dots in a dispersant containing reducing organic matter for preservation, and the reducing organic matter can eliminate and resist the generation of water, oxygen, light and other factors from the dispersant and the air.
  • the oxidation reaction factor can effectively ensure the fluorescence stability of the quantum dots during the storage process, and solve the problem of the reduction of the fluorescence quantum yield caused by the influence of water, oxygen, light and other factors during the storage process of the purified quantum dots.
  • the storage temperature is 20-30°C.
  • the quantum dot storage method described in this embodiment does not require low temperature (0° C.) storage, and long-term storage of quantum dots can also be achieved at room temperature.
  • the conditions of the quantum dot storage method described in this embodiment are set to a normal temperature of 25° C., an ambient humidity of 50%, and an environment of natural light.
  • the method for storing quantum dots can realize long-term storage of quantum dots, and the storage time is 1 to 15 weeks.
  • the quantum dots described in this example still maintain high fluorescence quantum efficiency after being stored for 15 weeks.
  • the quantum dot sample preservation method by adding an organic substance with weak reducibility to the purified quantum dot dispersant, the oxidation reaction factors generated by factors such as water, oxygen, light and the like from the dispersant and the air can be eliminated and resisted, At the same time, the added reducing organic matter is dissociated in the dispersant, which can fill in the defects caused by the shedding of weak ligands on the surface of the quantum dots in time, so as to ensure that the fluorescence quantum efficiency of the quantum dots does not change for a long time in the dispersant.
  • Example 1 The present disclosure provides a pair of Example 1, which is different from Example 1 in that no reducing organic tributylphosphine is added to Comparative Example 1, and the rest are the same.
  • the fluorescence quantum yield of the quantum dots of Comparative Example 1 decreases with the prolongation of the storage time, and the fluorescence intensity decreases continuously, from the initial fluorescence quantum yield of 85% to a stable 38%.
  • the fluorescence quantum yield of the addition of tributylphosphine decreased slightly to 80% in the early stage, and remained at a normal level with time. It can be seen that the water, oxygen and light in the normal temperature environment produce oxidation factors, which cause the fluorescence intensity of quantum dots to gradually decay, while the quantum dot fluorescence intensity of the quantum dot dispersion liquid with the addition of reducing organic matter is maintained better. It can be seen that the added reduction Sexual organic compounds play a role in protecting the fluorescence stability of quantum dots.
  • Example 2 which is different from Example 2 in that, in Comparative Example 2, no reducing organic ethanolamine is added, and the rest are the same.
  • the fluorescence quantum yield of the quantum dots of Comparative Example 2 decreased from the initial 60% to 15%, while the final fluorescence quantum yield of the quantum dots added with ethanolamine in Example 2 was as high as 55%.
  • Example 3 of the present disclosure deionized water was used as a dispersant to prepare 5 mL of CdSe/CdS/ZnS water-soluble quantum dots with 10 mmol/mL diethylenetriamine as the surface organic ligand, and 30 mmol of polyethylene glycol amine was added as a reducing agent.
  • Organic matter stored at 0°C in a refrigerator, and monitored the fluorescence stability of quantum dot samples.
  • Example 3 The present disclosure provides a pair of Example 3, the difference from Example 3 is that no reducing organic polyethylene glycol amine is added in Comparative Example 3, and the rest are the same.
  • Comparative Example 3 5 mL of 10 mmol/mL diethylenetriamine was selected as the CdSe/CdS/ZnS water-soluble quantum dots with surface organic ligands as the monitoring object. Due to the particularity of the aqueous solution, the problem of aggregation and sedimentation is likely to occur at room temperature. Therefore, it was stored in a low temperature refrigerator at 0°C. As shown in Table 1, the initial fluorescence quantum yield of the water-phase quantum dots in Comparative Example 3 was 33%. After the test cycle changes, the fluorescence intensity quenching of the comparison quantum dots was more obvious, and the final test value was 5%. In contrast, in Example 3, the fluorescence quantum yield of the quantum dot aqueous phase to which 30 mmol of polyethylene glycol amine was added was 26%.
  • sample preservation is set to normal temperature 25°C or 0°C, 50% ambient humidity, and natural light environment;
  • the fluorescence quantum yield test setting standard is periodic sampling to monitor the fluorescence quantum yield of the sample, and the test interval is 1 week, 1 week, 2 weeks, 3 weeks, 4 weeks, and 4 weeks. Three groups of samples were randomly selected from the parallel samples for determination.
  • Table 1 is the fluorescence quantum yield monitoring data of Examples 1-3 and Comparative Examples 1-3 provided by the present disclosure. As can be seen from Table 1, the storage method of quantum dots described in the present disclosure can effectively ensure the fluorescence stability of quantum dots for long-term storage.
  • the quantum dot dispersion described in the present disclosure contains organic substances with weak reducibility. On the one hand, it can eliminate the oxidation reaction factors introduced by factors such as temperature, illumination, and water and oxygen environment, avoid defects on the surface of the inorganic nanocrystals of quantum dots, and reduce the fluorescence quantum yield. On the other hand, the added reducing organic matter can act as a ligand on the surface of the quantum dot, and is in a free state in the dispersant. When the ligand on the surface of the quantum dot falls off due to the failure of the weak coordination bond, the surface of the quantum dot is replenished in time. defects, maintaining the fluorescence stability of quantum dots.

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Abstract

本公开涉及一种量子点分散液及量子点保存方法。所述量子点分散液包括：分散剂、量子点和还原性有机物。本公开所述量子点分散液中含有还原性有机物，该还原性有机物可以消除和抵抗来自分散剂和空气中的水、氧、光照等因素产生的氧化反应因子，从而有效保证量子点在保存过程中的荧光稳定性，解决经纯化后的量子点在保存过程中受水、氧、光等因素影响导致的荧光量子产率降低的问题。

Description

一种量子点分散液及量子点保存方法
优先权
本公开要求申请日为2020年12月28日，申请号为“202011583569.7”，申请名称为“一种量子点分散液及量子点保存方法”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及量子点技术领域，尤其涉及一种量子点分散液及量子点保存方法。
背景技术
量子点(量子点发光材料)一般由无机纳米晶体和形成在所述无机纳米晶体表面的表面配体组成，其中，所述无机纳米晶体可以是核壳结构无机纳米晶体。所述核壳结构无机纳米晶体具体包括量子点晶核、以及包覆所述量子点晶核的多壳层结构。所述量子点中，量子点晶核通过多壳层和表面配体连接，可以得到高荧光量子效率、稳定性较好的量子点发光材料。
在生产制备过程中，需要对合成得到量子点进行保存，具体是将合成得到量子点经过纯化后，分散到有机相、醇相或者水相溶剂中进行低温保存。但是，量子点发光材料在保存过程中会发生或快或慢的荧光量子产量衰减的问题。
因此，现有技术还有待于改进和发展。
公开内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点分散液及量子点保存方法，旨在解决量子点发光材料在保存过程中会发生荧光量子产量衰减的问题。
一种量子点分散液，其中，包括：分散剂、量子点和还原性有机物。
所述的量子点分散液，其中，所述还原性有机物选自醇类、酚类、醛类、有机胺类、 有机磷类、烯烃中的一种或多种；
所述还原性有机物选自乙醇胺、三丁基膦、聚乙二醇胺中的一种或多种。
所述的量子点分散液，其中，所述量子点为含有表面配体的量子点。
所述的量子点分散液，其中，所述表面配体包括羧基表面配体、胺基表面配体、巯基表面配体和膦基表面配体中的一种或多种。
所述的量子点分散液，其中，所述还原性有机物为含有配位基团的还原性有机物。
所述的量子点分散液，其中，所述配位基团包括羧基、胺基、巯基、膦基中的至少一种。
所述的量子点分散液，其中，所述配位基团与所述量子点的配位活性强于所述表面配体与所述量子点的配位活性。
所述的量子点分散液，其中，所述分散剂包括氯仿、甲苯、正己烷、环己烷、正庚烷、癸烷、正辛烷、环庚烷、二氧六环、水、甲醇、乙醇、异丙醇、正丁醇中的一种或多种；
所述还原性有机物与所述量子点的摩尔比为0.5:1～2:1；
所述量子点分散液中，所述量子点的浓度为1mmol/mL～100mmol/mL；
所述量子点选自II-VI族化合物量子点、IV-VI族化合物量子点、III-V族化合物量子点、I-VI族化合物量子点中的一种或多种。
所述的量子点分散液，其中，所述量子点为采用单层或多层半导体材料壳层包覆量子点晶核形成的核壳量子点。
所述的量子点分散液，其中，所述量子点晶核选自CdSe、CdS、CdTe、CdSeTe、CdZnS、PbSe、ZnTe、CdSeS、PbS、PbTe、HgS、HgSe、HgTe、GaN、GaP、GaAs、InP、InAs、InZnP、InGaP、InGaN、CdZnSe和CdZnSe中的至少一种。
所述的量子点分散液，其中，所述半导体材料壳层选自ZnSe、ZnS和ZnSeS中的至少一种。
所述的量子点分散液，其中，所述量子点为红色量子点CdZnSe/ZnSe/ZnS或绿色量子点CdZnSe/ZnS。
一种量子点保存方法，其中，包括：
将量子点、还原性有机物、分散剂配制成如权利要求1～8任一所述量子点分散液，对所述量子点进行保存。
所述的量子点保存方法，其中，所述保存的温度为20～30℃。
有益效果：本公开所述量子点分散液含有还原性有机物，该还原性有机物可以消除和抵抗来自分散剂和空气中的水、氧、光照等因素产生的氧化反应因子，从而有效保证量子点在保存过程中的荧光稳定性，解决量子点在保存过程中受水、氧、光等因素影响导致的荧光量子产率降低的问题。
具体实施方式
本公开提供一种量子点分散液及量子点保存方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本公开，并不用于限定本公开。
在对量子点进行保存时，将合成得到的量子点从包含反应溶剂、未转化前驱物和过量有机配体的反应体系中分离出来，得到由无机纳米晶体和有机表面配体组成的量子点，并将得到的量子点分散在溶剂中进行保存。发明人在研究量子点发光材料工作中发现，温度、光照和水氧环境等保存条件对量子点的光学性能和稳定性有重要影响。
通常根据表面配体性质的不同，将量子点无机纳米晶体分散在不同的溶剂中，所述溶剂可以是有机相、醇相或者水相溶剂。由于表面配体与量子点核壳结构是通过配位键方式连接，在分散剂中，表面配体容易从量子点核壳结构的无机纳米晶体的表面脱落使量子点的表面形成缺陷，当缺陷捕获一个电子或空穴时，它可以充当一个氧化还原反应的活性中心，所述反应中心会与空气中的水、氧发生反应，进而破坏量子点的荧光稳定性。
另外，在短波长紫外波段的光照下，量子点表面吸附来自于溶剂或者空气环境中的水分子，使量子点无机纳米晶体表面金属原子氧化从而产生缺陷，导致荧光量子效率降低。
同时，还发现经过纯化的量子点荧光强度随着存放温度的升高呈线性下降趋势，主要是由于不可逆辐射或者量子点无机纳米晶体表面氧化作用增强导致量子产率下降。
针对量子点纳米材料存放过程中荧光量子产率降低的问题，通过避光保存在惰性气氛环境下可以一定程度延缓量子点表面被水汽、氧气和光照等因素的侵蚀产生的不良影响，但是无法改善由于表面配体脱落产生的荧光量子产率降低的问题。另外，量子点苛刻的存放条件增加了额外的工艺成本。因此，亟需寻求一种可以有效改善量子点保存过程中荧光量子产率降低的解决办法。
经过研究，量子点经纯化后保存在有机相、醇相或者水相溶剂中，在受到环境的温度、光照和水氧等保存条件因素影响，会发生氧化等反应，干扰可移动电子和空穴的布局，导致不可逆的光致猝灭。其中，量子点表面吸附的水分子会氧化量子点表面，导致激子发射的蓝移，最终引入新的表面缺陷，降低了量子点的发光强度。量子点的光氧化将产生新的缺陷抑制激子的发射，从而导致较低的发光量子产率(发光QY)。在量子点晶核外层除了配位键连接的表面配体，宽带隙的壳层也有维持荧光量子产率的作用，但是宽带隙壳层在湿氧环境下，量子点表面受形成的氧自由基阴离子吸附物影响，导致电子波函数受限程度降低。另外，氧在量子点核壳间非平滑的能级梯度有一定渗透性，即使对于壳层较厚的量子点，氧分子可以通过核壳界面到达量子点晶核，产生缺陷空位降低荧光量子产率。
温度造成的光致发光性质的改变均是不可逆的，可能是因为温度的升高，导致了不可逆辐射的增强以及发生类似氧化等反应，从而致使荧光强度或量子产率降低以及发射峰位置的改变不能恢复到升温前的状态。
无论是温度还是光照、水氧的因素对量子点结构产生的破坏导致荧光量子产率的衰减，都与外部产生的氧化因子直接相关，本公开提出一种在分散剂中添加具有抗氧化效果的还原性有机物方法，将由温度或者光照、水氧等环境因素产生的氧化因子消除，避免由这些氧化因子引起的负电性氧自由基对量子点表面或者内部产生不可逆的破坏，导致荧光量子产率降低，影响量子点光电性能。
本公开实施例提供一种量子点分散液，其中，包括：分散剂、量子点和还原性有机 物。
本公开实施例通过在分散剂中添加还原性有机物，该还原性有机物可以消除和抵抗来自分散剂和空气中的水、氧、光照等因素产生的氧化反应因子，从而有效的保证量子点长久保存的荧光稳定性，可以有效解决量子点保存过程中受水、氧、光等因素影响导致的荧光量子产率降低的问题。
在本公开的一个实施方式中，所述还原性有机物是具有弱还原性的有机物，所述还原性有机物选自醇类、酚类、醛类、有机胺类、有机磷类、烯烃中的一种或多种。本实施例所述还原性有机物不限于上述种类的还原性有机物，例如所述还原性有机物还可以是其他含双键的化合物。在实施过程中，可以根据分散剂的不同，选择能够分散在相应分散剂的还原性有机物。
在本公开的一个实施方式中，所述的量子点分散液中，所述量子点为含有表面配体的量子点，所述量子点包括无机纳米晶体，以及结合在所述无机纳米晶体表面的有机配体。其中，所述表面配体包括羧基表面配体、胺基表面配体、巯基表面配体和膦基表面配体中的一种或多种。所述表面配体包括含有羧基、胺基、巯基和膦基的短链或长链有机物中的一种或多种，所述表面配体与无机纳米晶表面阳离子以配位键形式连接。举例地，所述表面配体可以为9-羧基-2-辛基芘、三辛基膦、十八烷基胺、十八硫醇等。
在研究过程中还发现，所述量子点的表面配体的脱落也是引起量子点表面缺陷的主要原因之一。量子点的表面配体的脱落后会对离域到表面的激子产生一定的淬灭效应导致荧光量子产率较低。在量子点无机纳米晶体的表面，由晶格缺陷产生的表面悬挂键，会影响量子点的光学性质。量子点无机纳米晶体表面性质对处于基态的量子点影响较小，但对激发态下的量子点性能影响巨大，量子点表面的缺陷存在，会引入缺陷态能级，当缺陷能级比激子能级低时，缺陷能级就可能捕获电子和空穴，然后激子通过缺陷态复合，能量以光或热的形式放出。通过表面配体对量子点表面的包覆，消除晶格缺陷，使量子点具有更好的荧光稳定性，一般来说，表面配体的选择更长链、更大空间位阻的表面配体。
在本公开的一个实施方式中，所述还原性有机物为含有配位基团的还原性有机物， 所述含有配位基团的还原性有机物是指所述还原性有机物的分子链上连接有配位基团，所述配位基团能够与所述无机纳米晶体表面阳离子形成配位键。可选地，所述表面配体包括羧基表面配体、胺基表面配体、巯基表面配体和膦基表面配体中的一种或多种，也即是所述配位基团包括羧基、胺基、巯基、膦基中的至少一种。本实施例所述还原性有机物中的羧基、胺基、巯基、膦基等配位基团可以对量子点表面由于有机配体脱落产生的晶格缺陷进行补位，避免由此产生的缺陷淬灭激子，降低荧光量子产率的问题。
在本公开的一个实施方式中，所述配位基团与所述量子点的配位活性强于所述表面配体与所述量子点的配位活性。也即是，选择的还原性有机物的配位活性强于表面配体的配位活性，其中，所述配位活性是指配位基团或表面配体与无机纳米晶体形成配位键的容易程度或形成配位键的稳定程度。本公开实施例通过选择比表面配体的配位活性更高的还原性有机物，能够在无机纳米晶体的表面形成更加稳定的配位键。
通常，配位基团的配位活性顺序为巯基>胺基>羧基>膦基，而对于相同的配位基团的配位活性顺序为短链>长链(含有配位基团的还原性有机物分子链越长，含有配位基团的还原性有机物配位活性越低)。在本公开的一个实施方式中，根据上述配位基团活性顺序选取比表面配体的配位活性更高的还原性有机物。
在本公开的一个实施方式中，所述还原性有机物选自乙醇胺、三丁基膦、聚乙二醇胺中的一种或多种。所述乙醇胺、三丁基膦、聚乙二醇胺具有还原性，能够消除由温度或者光照、水氧等环境因素产生的氧化因子；同时分别还含有胺基、膦基等配位基团，可以对量子点表面由于配体脱落产生的空位缺陷进行补位，避免荧光量子产率的降低。
在实施过程中，可以根据量子点分散剂不同，选择添加的还原性有机物需满足可分散在有机相、醇相或者水相溶剂中。通过选择在分散剂中具有良好溶解性的还原性有机物，从而形成均一稳定的量子点分散液，使所述还原性有机物能够在分散液中自由移动，有利于通过自由移动实现还原性有机物作为表面配体的形态与量子点无机纳米晶体表面成键，从而填补由于原位表面配体脱落产生的缺陷。举例地，可以相似相容的原理选择还原性有机物，如极性分散剂对应选取极性的还原性有机物，非极性的分散剂则选取非极性的还原性有机物。
本实施例所述分散剂用于分散量子点以及还原性有机物。所述量子点分散剂包括有机相溶剂、醇相溶剂或者水相溶剂。有机相溶剂可以为氯仿、甲苯、正己烷、环己烷、正庚烷、癸烷、正辛烷、环庚烷和二氧六环中的一种或多种；醇相溶剂可以为甲醇、乙醇、异丙醇、正丁醇等中的一种或多种；水相溶剂为去离子水。
本实施例所述分散剂可以为非极性溶剂，如二氯乙烷，也可以为极性溶剂，如水。
在本公开的一个实施方式中，所述还原性有机物与所述量子点的摩尔比为0.5:1～2:1。也即是，在分散剂中根据摩尔比为m(还原性有机物):m(量子点)＝0.5:1～2:1的方式添加，在研究过程中发现，当所述摩尔比小于0.5:1时，添加的还原性有机物偏少，对分散剂中氧化因子的消除和对量子点的表面配体的补充效果较差，根据测定的荧光量子产率数据，仍会明显的衰减；当所述摩尔比大于2:1时，过多的还原性有机物添加会影响量子点在分散剂中存在的形态，可能会在量子点表面形成有机物包覆层，影响量子点的应用。
本实施例所述还原性有机物与所述量子点的摩尔比为0.5:1～2:1，使得量子点表面存在一定程度的还原性环境下，避免量子点的荧光性能受环境中的温度、光照和水氧等保存条件因素引入的氧化因子影响，同时，分散剂中存在一定比例的表面配体可以与量子点表面脱落的有机配体形成动态补位缺陷的效果，减少由于表面缺陷产生的荧光不稳定性问题。
所述量子点选自II-VI族化合物量子点、IV-VI族化合物量子点、III-V族化合物量子点、I-VI族化合物量子点，也即是，所述量子点选自II-VI点、IV-VI、III-V、I-VI族化合物的单一结构量子点和复合结构量子点中的至少一种。在本公开的一个实施方式中，所述量子点为核壳量子点。核壳量子点为一种复合结构量子点，具体通过采用单层或多层半导体材料壳层包覆量子点晶核，举例地，所述量子点晶核选自CdSe、CdS、CdTe、CdSeTe、CdZnS、PbSe、ZnTe、CdSeS、PbS、PbTe、HgS、HgSe、HgTe、GaN、GaP、GaAs、InP、InAs、InZnP、InGaP、InGaN、CdZnSe和CdZnSe中的至少一种；半导体材料壳层选自ZnSe、ZnS和ZnSeS中的至少一种，所述量子点可以为红色量子点CdZnSe/ZnSe/ZnS或绿色量子点CdZnSe/ZnS。其中，量子点晶核与半导体材料壳层 间的晶格失配及能带偏差的调整改善量子点性能，一方面，核壳间晶格失配小有利于层核壳界面处形成合金过渡，减少晶格应力导致的界面缺陷形成无辐射复合中心；另一方面，核与壳间能带偏差大有利于电子和空穴波函数束缚在核内，远离壳层表面态的无辐射复合中心，所以通过多壳层的生长可以提高量子点的荧光稳定性和光电性能。
在本公开的一个实施方式中，所述量子点分散液中，所述量子点的浓度为1mmol/mL～100mmol/mL，所述量子点的浓度为5mmol/mL、40mmol/mL、80mmol/mL等。
本公开实施例提供一种量子点保存方法，其中，包括：
将量子点、还原性有机物、分散剂配制成如上所述量子点分散液，对所述量子点进行保存。
本实施例所述量子点保存方法是将量子点分散在含有还原性有机物的分散剂中进行保存，该还原性有机物可以消除和抵抗来自分散剂和空气中的水、氧、光照等因素产生的氧化反应因子，从而能够有效的保证量子点在保存过程中的荧光稳定性，解决经纯化后量子点在保存过程中受水、氧、光等因素影响导致的荧光量子产率降低的问题。
在本公开的一个实施方式中，所述保存的温度为20～30℃。本实施例所述量子点保存方法的无需要求低温(0℃)保存，在室温条件下也可以实现量子点的长期保存。本实施例所述量子点保存方法的条件设置为常温25℃，50％的环境湿度，自然光照的环境。
在本公开的一个实施方式中，所述量子点保存方法可以实现量子点的长时间保存，所述保存的时间为1周～15周。本实施例所述量子点在保存15周后仍保持高荧光量子效率。
所述量子点样品保存方法中，通过在纯化后的量子点分散剂中添加具有弱还原性的有机物，可以消除和抵抗来自分散剂和空气的水、氧、光照等因素产生的氧化反应因子，同时添加的还原性有机物游离分散在分散剂中，能够及时填充量子点表面弱配体脱落产生的缺陷，保证量子点在分散剂长时间荧光量子效率不变化。
下面通过具体的实施例和对比例对本公开的技术方案进行说明。
在本公开实施例1中，分散剂为氯仿，取5mL 50mmol/mL红色量子点 CdZnSe/ZnSe/ZnS(PL＝625nm，FWHM＝22nm)置于白色透明玻璃瓶中，有机配体为油酸、油胺，添加的还原性有机物为150mmol的三丁基膦，在常温25℃，50％的环境湿度，自然光照的存放条件下，监测样品荧光强度变化。
本公开提供一对比例1，与实施例1的区别为，对比例1未添加还原性有机物三丁基膦，其余相同。
由表1可知，从得到的数据可知，对比例1量子点的荧光量子产率随着存放时间的延长，荧光强度不断衰减，从初始的荧光量子产率85％下降到趋于稳定的38％。而添加了三丁基膦的荧光量子产率在前期有小幅降低到80％，随着时间延长一直处于正常波动的水平。可见，在常温环境下的水、氧、光照产生了氧化因子，致使量子点的荧光强度逐渐衰减，而添加了还原性有机物的量子点分散液的量子点荧光强度保持较好，可知添加的还原性有机物起到了保护量子点荧光稳定性作用。
本公开实施例2中，选取分散在5mL乙醇溶剂中的绿色量子点CdZnSe/ZnS(PL＝535nm，FWHM＝24nm)，浓度30mmol/mL，量子点表面有机配体为6-巯基己醇，添加100mmol乙醇胺作为还原性有机物。监测量子点样品的荧光稳定性。
本公开提供一对比例2，与实施例2的区别为，对比例2未添加还原性有机物乙醇胺，其余相同。
如表1所示，对比例2的量子点的荧光量子产率从初始60％下降到15％，而实施例2添加了乙醇胺的量子点最终荧光量子产率高达55％。
本公开实施例3中，采用去离子水为分散剂，配制5mL 10mmol/mL二乙烯三胺作为表面有机配体的CdSe/CdS/ZnS水溶性量子点，添加30mmol聚乙二醇胺作为还原性有机物，在冰箱中低温0℃保存，监测量子点样品的荧光稳定性。
本公开提供一对比例3，与实施例3的区别为，对比例3未添加还原性有机物聚乙二醇胺，其余相同。
对比例3中，选取5mL 10mmol/mL二乙烯三胺作为表面有机配体的CdSe/CdS/ZnS水溶性量子点作为监测对象，由于水相溶液的特殊性，常温状态下容易产生聚集沉降问题，故置于低温冰箱0℃保存。如表1所示，对比例3中水相量子点的初始荧光量子产 率为33％，经过测试周期变化，对比量子点的荧光强度淬灭较为明显，最终测试值为5％。而实施例3在添加30mmol聚乙二醇胺的量子点水相的荧光量子产率为26％。
实施例1～3和对比例1～3中，所述监测量子点分散液的荧光稳定性按照以下流程进行：
(1)、分别选取10组平行条件下分散在有机相、醇相和水相溶剂中的量子点溶液；
(2)、样品保存的条件设置为常温25℃或0℃，50％的环境湿度，自然光照的环境；
(3)、荧光量子产率测试设置标准为周期取样监测样品的荧光量子产率，测试间隔时间为1周、1周、2周、3周、4周、4周，测试取样按照从10组平行样品中随机抽取3组样品进行测定。
表1是本公开提供的实施例1～3和对比例1～3荧光量子产率监测数据。如表1可知，本公开所述量子点的保存方法能够有效保证量子点长久保存的荧光稳定性。
表1：本公开提供的实施例和对比例荧光量子产率监测数据
Figure PCTCN2021140506-appb-000001
Figure PCTCN2021140506-appb-000002
本公开所述量子点分散液中含有具有弱还原性的有机物，一方面可以消除由于温度、光照和水氧环境等因素引入的氧化反应因子，避免量子点无机纳米晶体表面产生缺陷降低荧光量子产率；另外一方面，添加的还原性有机物可以充当量子点表面配体的作用，在分散剂中处于游离态，当量子点表面配体由于弱配位键失效脱落时，及时补位量子点表面形成的缺陷，保持量子点荧光稳定性。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。

Claims (18)

  1. 一种量子点分散液，其中，包括：分散剂、量子点和还原性有机物。
  2. 根据权利要求1所述的量子点分散液，其中，所述还原性有机物选自醇类、酚类、醛类、有机胺类、有机磷类、烯烃中的一种或多种。
  3. 根据权利要求2所述的量子点分散液，其中，所述还原性有机物选自乙醇胺、三丁基膦、聚乙二醇胺中的一种或多种。
  4. 根据权利要求1所述的量子点分散液，其中，所述量子点为含有表面配体的量子点。
  5. 根据权利要求4所述的量子点分散液，其中，所述表面配体包括羧基表面配体、胺基表面配体、巯基表面配体和膦基表面配体中的一种或多种。
  6. 根据权利要求5所述的量子点分散液，其中，所述还原性有机物为含有配位基团的还原性有机物。
  7. 根据权利要求6所述的量子点分散液，其中，所述配位基团包括羧基、胺基、巯基、膦基中的至少一种。
  8. 根据权利要求7所述的量子点分散液，其中，所述配位基团与所述量子点的配位活性强于所述表面配体与所述量子点的配位活性。
  9. 根据权利要求1所述的量子点分散液，其中，所述分散剂包括氯仿、甲苯、正己烷、环己烷、正庚烷、癸烷、正辛烷、环庚烷、二氧六环、水、甲醇、乙醇、异丙醇、正丁醇中的一种或多种。
  10. 根据权利要求9所述的量子点分散液，其中，所述还原性有机物与所述量子点的摩尔比为0.5:1～2:1。
  11. 根据权利要求10所述的量子点分散液，其中，所述量子点分散液中，所述量子点的浓度为1mmol/mL～100mmol/mL。
  12. 根据权利要求11所述的量子点分散液，其中，所述量子点选自II-VI族化合物量子点、IV-VI族化合物量子点、III-V族化合物量子点、I-VI族化合物量子点中的一种或多种。
  13. 根据权利要求12所述的量子点分散液，其中，所述量子点为采用单层或多层半 导体材料壳层包覆量子点晶核形成的核壳量子点。
  14. 根据权利要求13所述的量子点分散液，其中，所述量子点晶核选自CdSe、CdS、CdTe、CdSeTe、CdZnS、PbSe、ZnTe、CdSeS、PbS、PbTe、HgS、HgSe、HgTe、GaN、GaP、GaAs、InP、InAs、InZnP、InGaP、InGaN、CdZnSe和CdZnSe中的至少一种。
  15. 根据权利要求13所述的量子点分散液，其中，所述半导体材料壳层选自ZnSe、ZnS和ZnSeS中的至少一种。
  16. 根据权利要求13所述的量子点分散液，其中，所述量子点为红色量子点CdZnSe/ZnSe/ZnS或绿色量子点CdZnSe/ZnS。
  17. 一种量子点保存方法，其中，包括：
    将量子点、还原性有机物、分散剂配制成如权利要求1～12任一所述量子点分散液，对所述量子点进行保存。
  18. 根据权利要求17所述的量子点保存方法，其中，所述保存的温度为20～30℃。
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