WO2019161588A1 - 量子点复合物、其制备方法和量子点复合物分散体系 - Google Patents

量子点复合物、其制备方法和量子点复合物分散体系 Download PDF

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WO2019161588A1
WO2019161588A1 PCT/CN2018/080189 CN2018080189W WO2019161588A1 WO 2019161588 A1 WO2019161588 A1 WO 2019161588A1 CN 2018080189 W CN2018080189 W CN 2018080189W WO 2019161588 A1 WO2019161588 A1 WO 2019161588A1
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quantum dot
dot composite
quantum
coating
ligand
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PCT/CN2018/080189
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French (fr)
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李鑫
王允军
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苏州星烁纳米科技有限公司
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    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor

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  • This application belongs to the field of chemistry, and in particular relates to a quantum dot composite.
  • the invention also relates to a process for the preparation of such quantum dot composites.
  • the invention also relates to quantum dot composite dispersion systems.
  • Quantum dots also known as semiconductor nanocrystals, have a very narrow half-width of the emission spectrum, and thus have a very wide range of applications in the fields of electroluminescence, photoluminescence, and biomarkers.
  • quantum dots are susceptible to adverse effects of the external environment, which in turn leads to weakening of the light-emitting intensity of the quantum dot light-emitting device.
  • a quantum dot composite according to the first aspect of the present invention comprises a quantum dot and a coating of a coated quantum dot, the cladding being composed of three components of a metal element, a hydrogen element, and an oxygen element and insoluble in water.
  • the inventors have unexpectedly discovered that the coating consisting of three components of metal element, hydrogen element and oxygen element in the present application has a long life in a photoluminescence environment, and the coating does not cause photoreception of quantum dots.
  • the luminescence property causes an adverse effect, so that the light-emitting intensity of the quantum dot composite according to the present application has little attenuation with time, and the quantum dot composite is stable and has a long life.
  • the coating is a mixture of one or more of aluminum hydroxide, titanium hydroxide, aluminum oxyhydroxide, and titanium oxyhydroxide.
  • it usually does not contain strong acid or strong alkali, so the coating has good chemical stability, so the coating can protect the quantum dots well, making the stability of the quantum dot composite very Good, long life.
  • aluminum hydroxide ie, Al(OH) 3
  • aluminate ie, H 3 AlO 3
  • the number of quantum dots coated within the cladding is one.
  • the quantum dots have good luminescence properties and long lifetime, which is not only useful for fabricating photoluminescent devices, but also for fabricating quantum dot inks and electroluminescent devices. help.
  • the number of quantum dots coated is two or more.
  • the inventors have unexpectedly discovered that when the number of coated quantum dots is two or more, for example, five, eight, or ten, the quantum dot composite has almost the same light intensity as the quantum dots, and the stability is also Can be improved. In addition, this greatly reduces the difficulty in preparing quantum dot composites.
  • two or more quantum dots are separated. In this case, the quantum dots are separated from each other (i.e., not in contact with each other), which is more conducive to increasing the light-emitting intensity of the quantum dot composite.
  • the thickness of the cladding is between 2 nm and 45 nm.
  • the inventors have unexpectedly found that in this case, the stability of the quantum dot complex is very good, and the light intensity is less attenuated with time.
  • the thickness of the coating is less than 2 nm, the coating is difficult to protect the quantum dots, resulting in a shortened life of the quantum dot composite and poor stability.
  • the thickness of the coating is greater than 45 nm, the light intensity of the quantum dot composite deteriorates.
  • the quantum dot composite has a particle size between 15 nm and 100 nm.
  • the inventors have found that when the particle size of the equivalent sub-point complex is less than 15 nm, the quantum dots are not completely coated by the coating, resulting in a shortened life of the quantum dot composite and poor stability.
  • the particle size of the quantum dot composite is larger than 100 nm, the dispersibility of the quantum dot composite is deteriorated, so that it is difficult to form a quantum dot composite film layer having a uniform thickness, which is very disadvantageous for fabricating a device.
  • a method of preparing a quantum dot composite comprising the steps of: step 1): adding a metal alkoxide to an organic solvent containing quantum dots to form a first system, step 2) : introducing water into the first system, step 3): after step 2), reacting in the first system to form a quantum dot composite comprising quantum dots and a coating of coated quantum dots, the package
  • the covering consists of three components of a metal element, a hydrogen element, and an oxygen element and is insoluble in water.
  • the metal alkoxide is hydrolyzed in the presence of water, and nucleates and grows on the quantum dots, thereby producing three kinds of metal elements, hydrogen elements and oxygen elements on the quantum dots.
  • the method of the present invention has broad applicability to different quantum dots, for example, for the following quantum dots: CdSe, CdZnSe, CdZnSeS, CdSe/ZnS, CdZnSe/CdZnS/ZnS, InP, InP/ZnS, carbon Quantum dots, Au quantum dots, Cu quantum dots, gradient alloy quantum dots, perovskite quantum dots, and the like.
  • step 1) the metal alkoxide is first dissolved in a liquid alkane to form a second system, and then the second system is added to the organic solvent of the quantum dot.
  • the inventors have found that the preparation of a metal alkoxide and a liquid alkane into a second system can greatly improve the solubility of the metal alkoxide in an organic solvent containing quantum dots, thereby contributing to the preparation of a good quality quantum dot composite.
  • the liquid alkane is a C5 to C10 alkane, or a C5 to C8 cycloalkane.
  • the organic solvent containing quantum dots is toluene, or a C5 to C13 alkane, or a C5 to C8 cycloalkane.
  • step 2) a mixed gas of water vapor and an inert gas is introduced into the first system to introduce water into the first system.
  • the amount of water introduced can be conveniently controlled to avoid excessive water damage to the quantum dots; in addition, the reaction rate can be conveniently controlled to obtain a high quality quantum dot composite.
  • the inert gas also protects the quantum dots from oxygen damage.
  • the inert gas containing water vapor has a humidity of between 33% and 48%, preferably 40%.
  • the inventors have unexpectedly discovered that at this humidity, the quantum dot complex is formed at a slower rate, thereby contributing to the improvement of the compactness of the coating and the easy control of the thickness of the coating and the particle size of the quantum dot composite. Not only helps to improve the protection of the quantum dots by the coating, but also does not affect the luminescent properties of the quantum dot composite.
  • the metal alkoxide is a saturated metal alkoxide of C3 or C4.
  • it may be a mixture of one or more of aluminum isopropoxide, aluminum sec-butoxide, titanium isopropoxide, and titanium t-butoxide.
  • a quantum dot composite dispersion system comprising: a non-polar organic solvent, and a quantum dot composite dispersed in a non-polar organic solvent, the quantum dot composite comprising quantum dots, a cladding layer formed on the outer surface of the quantum dot, and a first ligand attached to the cladding layer.
  • the first ligand has a first group attached to the coating and a second group that is affinity with the non-polar organic solvent.
  • the coating layer can protect the quantum dots, and the first ligand has a second group which is affinity with the non-polar organic solvent, so that the quantum dot composite not only has good stability, but also is soluble in common A non-polar organic solvent makes it possible to use such a quantum dot composite well.
  • the coating layer is a mixture of one or more of aluminum hydroxide, titanium hydroxide, aluminum oxyhydroxide, and titanium oxyhydroxide.
  • the first group is a carboxyl group or an amino group. The inventors have unexpectedly discovered that a stable linkage can be rapidly formed between a carboxyl group or an amino group and such a coating layer, and that such a connection is formed without heating, a special catalyst, and an extreme acid-base ring property, which makes it even contain a carboxyl group or an amino group.
  • the ligand is directly added to the dispersion containing the quantum dot complex, and the ligand can be quickly and automatically attached to the quantum dot complex, which greatly simplifies the experimental operation.
  • the second group is a C6-C22 aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group further has a substituent group
  • the substituted group is a substituted or unsubstituted C4-C22 alicyclic hydrocarbon group, and/or a substituted or unsubstituted C6-C22 aromatic group. Hydrocarbyl group.
  • a substituent selected from the group consisting of hydroxy (-OH), amino (-NRR', wherein R and R' Independently hydrogen or C1-C6 alky
  • the first ligand is oleic acid or oleylamine.
  • the non-polar organic solvent is toluene or a liquid alkane.
  • the quantum dot composite is present in an amount of from 1.2% to 3.6% by mass, and the first ligand is present in an amount of from 2% to 4% by mass, the balance being the non-polar organic solvent. It is generally believed that the greater the amount of the first ligand, the more advantageous the dissolution of the quantum dot complex in a non-polar solvent. However, the inventors have unexpectedly discovered that in the scheme of the present application, the content of the first ligand in the quantum dot complex dispersion is not linearly related to the solubility of the quantum dot complex in the dispersion.
  • the content of the quantum dot complex is 1.2%-3.6% by mass, and the content of the first ligand is less than 2%, some quantum dot complexes may not dissolve; and when the content of the first ligand is more than 4% At the same time, some quantum dot composites will precipitate.
  • the content of the quantum dot composite is 1.2%-3.6% by mass, the content of the first ligand is 2%-4%, and the balance is the non-polar organic solvent, the quantum dot complex can be stabilized. Dissolved in a non-polar solvent to form a stable quantum dot composite dispersion.
  • the surface of the quantum dot is also coupled to a second ligand, the cladding covering the second ligand.
  • the second ligand is one or more of oleic acid, oleylamine, thiol, trioctylphosphine oxide, trioctylphosphine.
  • a ligand (which is equivalent to the second ligand in the present application) is usually attached to the surface to enable the quantum dot complex to be stably dispersed or dissolved in a solvent. In the solution of the present application, even if the second ligand is present, the coating layer and the first ligand are not adversely affected, thereby greatly simplifying the preparation of the quantum dot composite dispersion system of the present application.
  • the advantages of the present application are as follows: (1)
  • the coating composed of the three components of the metal element, the hydrogen element and the oxygen element of the present application has good stability in a photoluminescence environment, and this pair
  • the quantum dots play a good protective role, which makes the quantum dot composites have better stability and longer lifetime, and the coating does not adversely affect the photoluminescence properties of the quantum dots, so that the quantum dot composite has not only Longer life, and the intensity of light output decays little with time.
  • the coating of the quantum dot complex can protect the quantum dot complex, and the first ligand has a second group that is affinity with the non-polar organic solvent, so that the quantum dot composite not only has good It is stable and soluble in common non-polar organic solvents, so that such quantum dot composites can be used well.
  • Figure 1 is a TEM photograph of Sample 1
  • Figure 2 is a TEM photograph of Sample 2
  • Figure 3 is a TEM photograph of Sample 3
  • Figure 4 is a TEM photograph of Sample 4.
  • Figure 5 is a TEM photograph of Sample 5
  • Figure 6 is a TEM photograph of Sample 6.
  • Figure 7a is a TEM photograph of the sample of Example 7.
  • Figure 7b is an emission spectrum of the quantum dot composite of Example 7 before and after dissolution
  • Figure 8a is a TEM photograph of the sample of Example 8.
  • Figure 8b is an emission spectrum of the quantum dot composite of Example 8 before and after dissolution
  • Figure 9a is a TEM photograph of the sample of Example 9;
  • Figure 9b is an emission spectrum of the quantum dot composite of Example 9 before and after dissolution
  • Figure 10a is a TEM photograph of a sample of Example 10.
  • Figure 10b is an emission spectrum of the quantum dot composite of Example 10 before and after dissolution.
  • a solution of aluminum isopropoxide in cyclohexane was prepared to form a second system at a concentration of 0.2 g/ml.
  • a toluene solution of red light CdSe was prepared at a concentration of 2 mg/ml.
  • a sample 1 of the quantum dot composite 5 ml of the second system was taken, 100 ml of a toluene solution of CdSe was taken, and then the second system was added to a toluene solution of CdSe to form a first system.
  • argon gas having a humidity of 40% was introduced into the first system to obtain a sample 1 of the quantum dot composite, and a TEM photograph is shown in Fig. 1.
  • the dark portions 12, 13, 15 are quantum dots, and the light colored portions 11, 14 are wraps.
  • the two quantum dots 12, 13 are coated together and the quantum dots 15 are individually coated.
  • the light intensity of sample 1 was tested using the CL-200FZ source photoelectric performance comprehensive test system produced by Hangzhou Kexing Photoelectric Co., Ltd.
  • the test conditions were as follows: the operating current of the test system was 20 mA, and the excitation wavelength was 460 nm.
  • the light intensity value obtained at each predetermined time is compared with the light intensity value at the initial time (that is, at 0 hours), and the results obtained are shown in Table 1.
  • a hexane solution of aluminum isopropoxide was prepared to form a second system at a concentration of 0.18 g/ml.
  • a toluene solution of red CdZnSe was prepared at a concentration of 1 mg/ml.
  • the light intensity of the sample 2 was tested, and the results are shown in Table 1.
  • the test methods and conditions are the same as in the first embodiment.
  • a pentane solution of aluminum sec-butoxide was prepared to form a second system at a concentration of 0.25 g/ml.
  • a solution of red light InP in n-heptane was prepared at a concentration of 5 mg/ml.
  • the light intensity of the sample 3 was tested, and the results are shown in Table 1.
  • the test methods and conditions are the same as in the first embodiment.
  • An octane solution of titanium t-butoxide was prepared to form a second system at a concentration of 0.3 g/ml.
  • a solution of red light CdSe/ZnS in cyclohexane was prepared at a concentration of 8 mg/ml.
  • the light intensity of the sample 4 was tested, and the results are shown in Table 1.
  • the test methods and conditions are the same as in the first embodiment.
  • An octane solution of titanium isopropoxide was prepared to form a second system at a concentration of 0.15 g/ml.
  • a solution of red light InP in cyclooctane was prepared at a concentration of 10 mg/ml.
  • the light intensity of the sample 5 was tested, and the results are shown in Table 1.
  • the test methods and conditions are the same as in the first embodiment.
  • An octane solution of titanium isopropoxide and aluminum t-butoxide was prepared to form a second system, and the total concentration of titanium isopropoxide and aluminum t-butoxide was 0.2 g/ml.
  • a solution of red light InP in cyclooctane was prepared at a concentration of 10 mg/ml.
  • the light intensity of the sample 6 was tested, and the results are shown in Table 1.
  • the test methods and conditions are the same as in the first embodiment.
  • the unexposed red InP quantum dots were used as Comparative Sample 1, and the light intensity of Comparative Sample 1 was tested. The results are shown in Table 1. The test methods and conditions are the same as in the first embodiment.
  • the unexposed red light CdSe/ZnS quantum dots were used as Comparative Sample 2, and the light intensity of Comparative Sample 2 was tested. The results are shown in Table 1. The test methods and conditions are the same as in the first embodiment.
  • the quantum dot composite of the present invention is still greater than or equal to the initial light intensity after being excited by a long time of irradiation. For example, after 500 hours of blue light illumination, the intensity of the light is still at least 100%. The light intensity is greatly improved compared to the uncoated quantum dots in the prior art. This demonstrates that the quantum dot composite of the present invention has a long lifetime and good photoluminescence properties.
  • quantum dot complex CdSe/Al(OH) 3 120 mg was selected , that is, the quantum dot was CdSe and the cladding layer was Al(OH) 3 .
  • the second ligand is oleic acid.
  • the non-polar organic solvent was toluene in a volume of 5 ml.
  • the quantum dot composite is mixed with toluene to form a first mixed system. At this time, the quantum dot complex exists as a precipitate in toluene.
  • the emission spectrum (i.e., PL) of the quantum dot composite before and after dissolution was also tested using a fluorescence spectrometer, as shown in Figure 7b.
  • curve 73 is the emission spectrum of the quantum dot complex prior to dissolution
  • curve 74 is the emission spectrum of the quantum dot complex after dissolution. It can be seen from Fig. 7b that the quantum dot complex has little change in the emission spectrum before and after dissolution, thereby contributing to the use of the quantum dot complex.
  • the second ligand is n-dodecyl mercaptan.
  • the non-polar organic solvent is n-octane and has a volume of 6 ml.
  • the quantum dot complex is mixed with n-octane to form a first mixed system. At this time, the quantum dot complex exists as a precipitate in n-octane.
  • the emission spectrum (i.e., PL) of the quantum dot complex before and after dissolution was also tested using a fluorescence spectrometer, as shown in Figure 8b.
  • curve 83 is the emission spectrum of the quantum dot complex prior to dissolution
  • curve 84 is the emission spectrum of the quantum dot complex after dissolution. It can be seen from Fig. 8b that the quantum dot complex has little change in the emission spectrum before and after dissolution, thereby contributing to the use of the quantum dot composite.
  • quantum dot complex CdS/Al(OH) 3 48 mg was selected , that is, the quantum dot was CdS and the cladding layer was Al(OH) 3 .
  • the second ligand is oleylamine.
  • the non-polar organic solvent was chloroform in a volume of 4 ml.
  • the quantum dot complex and chloroform are mixed to form a first mixed system. At this time, the quantum dot complex exists as a precipitate in chloroform.
  • the emission spectrum (i.e., PL) of the quantum dot complex before and after dissolution was also tested using a fluorescence spectrometer, as shown in Figure 9b.
  • curve 93 is the emission spectrum of the quantum dot complex prior to dissolution
  • curve 94 is the emission spectrum of the quantum dot complex after dissolution. It can be seen from Fig. 9b that the quantum dot complex has little change in the emission spectrum before and after dissolution, thereby contributing to the use of the quantum dot composite.
  • quantum dot complex ZnSe/Al(OH) 3 144 mg was selected , that is, the quantum dots were ZnSe and the cladding layer was Al(OH) 3 .
  • the second ligand is trioctyloxyphosphorus.
  • the non-polar organic solvent was n-heptane in a volume of 4 ml.
  • the quantum dot complex and n-heptane are mixed to form a first mixed system. At this time, the quantum dot complex exists as a precipitate in n-heptane.
  • the emission spectrum (i.e., PL) of the quantum dot complex before and after dissolution was also tested using a fluorescence spectrometer, as shown in Figure 10b.
  • curve 103 is the emission spectrum of the quantum dot complex prior to dissolution
  • curve 104 is the emission spectrum of the quantum dot complex after dissolution. It can be seen from Fig. 10b that the quantum dot complex has little change in the emission spectrum before and after dissolution, thereby contributing to the use of the quantum dot composite.

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Abstract

本发明涉及量子点复合物、其制备方法和量子点复合物分散体系。本发明的量子点复合物包括量子点和包覆所述量子点的包覆物，该包覆物由金属元素、氢元素、氧元素三种成分组成并且不溶于水。包覆物在光致发光环境中具有较长的寿命，并且包覆物不会对量子点的光致发光性能造成不良影响，根据本申请的量子点复合物不但具有较长的寿命，而且具有良好的光致发光性能。

Description

量子点复合物、其制备方法和量子点复合物分散体系
相关申请的交叉引用
本申请要求享有于2018年2月22提交的中国专利申请“201810153299.2”和2018年3月5日提交的中国专利申请“201810175910.1”的优先权，其全文内容以引用方式结合到本申请中。
技术领域
本申请属于化学领域，特别涉及一种量子点复合物。本发明还涉及这种量子点复合物的制备方法。本发明还涉及量子点复合物分散体系。
背景技术
量子点又称为半导体纳米晶，其发射光谱的半峰宽非常窄，因此在电致发光领域、光致发光领域以及生物标记等领域具有非常广泛的用途。
然而，在光致发光领域的使用中发现，量子点易受到外界环境的不良影响，进而导致量子点发光器件的出光强度变弱。
发明内容
针对上述技术问题，本申请提供一种量子点复合物。这种量子点复合物在光致发光领域中应用时，出光强度随时间的延长衰减很小，量子点的稳定性较好。此外，本申请还提供了制备这种量子点复合物的方法和量子点复合物分散体系。根据本发明的第一方面的量子点复合物，包括量子点和包覆量子点的包覆物，该包覆物由金属元素、氢元素、氧元素三种成分组成并且不溶于水。
发明人意外发现，本申请中的由金属元素、氢元素、氧元素三种成分组成的包覆物在光致发光环境中具有较长的寿命，并且包覆物不会对量子点的光致发光性能造成不良影响，这样根据本申请的量子点复合物的出光强度随着时间延长衰减很小，量子点复合物很稳定，具有较长的寿命。
在一个实施例中，包覆物为氢氧化铝、氢氧化钛、羟基氧化铝和羟基氧化钛中的一种或多种的混合。在光致发光环境中，通常不含有强酸或强碱，因此包覆 物具有良好的化学稳定性，从而包覆物会对量子点起到良好的保护作用，使得量子点复合物的稳定性很好，寿命较长。应理解的是，在本申请中，氢氧化铝(即，Al(OH) 3)也可以称之为铝酸(即，H 3AlO 3)，两者具有相同的化学结构和相同的作用；对于氢氧化钛也是如此，这里不再赘述。
在一个实施例中，包覆在包覆物内的量子点的数量为一个。当被包覆的量子点的数量为一个时，量子点具有良好的发光性能和较长的寿命，这不但对于制作光致发光器件有帮助，而且对于制作量子点墨水和电致发光器件非常有帮助。
在一个优选的实施例中，所包覆的量子点的数量为两个或更多个。发明人意外发现，当所包覆的量子点的数量为两个或更多个，例如5个、8个、10个时，量子点复合物具有与量子点几乎相同的出光强度，并且稳定性也得以提高。此外，这极大地降低了量子点复合物的制备难度。更优选地，两个或更多个的量子点彼分开。在这种情况下，量子点彼此分开(即，相互不接触)，这更加有助于提高量子点复合物的出光强度。
在一个优选的实施例中，包覆物的厚度在2nm到45nm之间。发明人意外发现，在这种情况下，量子点复合物的稳定性非常好，而且出光强度随时间延长衰减很小。当包覆物的厚度小于2nm时，包覆物难以对量子点起到保护作用，导致量子点复合物的寿命变短，稳定性变差。当包覆物的厚度大于45nm时，量子点复合物的出光强度会变差。
在一个实施例中，量子点复合物的粒径在15nm到100nm之间。发明人发现，当量子点复合物的粒径小于15nm时，实际上量子点并没有被包覆物彻底包覆上，从而导致量子点复合物的寿命变短，稳定性较差。当量子点复合物的粒径大于100nm时，量子点复合物的分散性会变差，从而难以形成厚度均匀的量子点复合物膜层，这非常不利于制备器件。
在一个实施例中，在包覆物的外表面上无有机物配体。
根据本发明的第二方面，提出了一种制备量子点复合物的方法，包括以下步骤，步骤1)：将金属醇盐加入到含有量子点的有机溶剂中，形成第一体系，步骤2)：向第一体系内引入水，步骤3)：在步骤2)之后，第一体系内反应生成量子点复合物，该量子点复合物包括量子点和包覆量子点的包覆物，该包覆物由金属元素、氢元素、氧元素三种成分组成并且不溶于水。
发明人发现，根据本发明的方法，金属醇盐在存在水的环境中发生水解，并且在量子点上形核、长大，从而在量子点上产生由金属元素、氢元素、氧元素三种成分组成的包覆物。发明人进一步发现，本发明的方法对于不同的量子点具有广泛的适用性，例如适用于以下量子点：CdSe、CdZnSe、CdZnSeS、CdSe/ZnS、CdZnSe/CdZnS/ZnS、InP、InP/ZnS、碳量子点、Au量子点、Cu量子点、梯度合金量子点、钙钛矿量子点等。
在一个实施例中，在步骤1)中，首先将金属醇盐溶解在液态烷烃中形成第二体系，然后将第二体系加入到量子点的有机溶剂中。发明人发现，在将金属醇盐和液态烷烃制备成第二体系，可以极大地提高金属醇盐在含有量子点的有机溶剂中的溶解度，从而有助于制备出品质良好的量子点复合物。
在一个实施例中，液态烷烃为C5到C10的烷烃，或C5到C8的环烷烃。在另一个实施例中，含有量子点的有机溶剂为甲苯、或C5到C13的烷烃，或C5到C8的环烷烃。这些液态烷烃和有机溶剂均为非极性的液态有机物，能够彼此互溶，这有助于提高金属醇盐在含有量子点的有机溶剂中的溶解度。
在一个实施例中，在步骤2)中，将水蒸气与惰性气体的混合气体通入到第一体系中，以向第一体系内引入水。通过这种方法，可以方便地控制所引入的水的量，从而避免过多的水破坏量子点；此外还可以方便地控制反应速度，从而得到高品质的量子点复合物。惰性气体也可以对量子点起到保护作用，避免其受到氧气的破坏。
在一个优选的实施例中，含有水蒸气的惰性气体的湿度在33％到48％之间，优选为40％。发明人意外发现，在这种湿度下，量子点复合物的生成速率较慢，从而有助于提高包覆物的致密性而且易于控制包覆物的厚度和量子点复合物的粒径，这样不但有助于提高包覆物对量子点的保护作用而且不影响量子点复合物的发光性能。
在一个实施例中，金属醇盐为C3或C4的饱和金属醇盐。例如，可以为异丙醇铝、仲丁醇铝、异丙醇钛和叔丁醇钛中的一种或多种的混合。
根据本发明的第三方面，提出了一种量子点复合物分散体系，包括：非极性有机溶剂，和分散在非极性有机溶剂中的量子点复合物，量子点复合物包括量子点、形成在量子点外表面上的包覆层、连接在包覆层上的第一配体。第一配体具有与包覆层相连的第一基团和与非极性有机溶剂亲和的第二基团。
包覆层能对量子点起到保护作用，而第一配体具有与非极性有机溶剂亲和的第二基团，这样量子点复合物不但具有良好的稳定性，而且能溶于常见的非极性有机溶剂，从而可以良好地使用这种量子点复合物。
在一个实施例中，包覆层为氢氧化铝、氢氧化钛、羟基氧化铝和羟基氧化钛中的一种或多种的混合。在另一个实施例中，第一基团为羧基或氨基。发明人意外发现，羧基或氨基与这种包覆层之间能快速形成稳定的连接，而且形成这种连接无需加热、特殊的催化剂、极端的酸碱环性，这使得甚至将含有羧基或氨基的配体直接加入到含有量子点复合物的分散系中，配体就能够快速自动连接到量子点复合物上，这极大地简化了实验操作。
在一个实施例中，第二基团为C6-C22的脂肪族烃基。
在一个优选的实施例中，脂肪族烃基上还具有取代基团，取代基团为取代或不取代的C4-C22的脂环族烃基，和/或取代或不取代的C6-C22的芳香族烃基。
在本申请中，术语“取代(的)”指的是其中其氢原子的至少一个被选自如下的取代基代替的化合物、基团或部分：C1-C30烷基、C2-C30炔基、C6-C30芳基、C7-C30烷芳基、C1-C30烷氧基、C1-C30杂烷基、C3-C30杂烷芳基、C3-C30环烷基、C3-C15环烯基、C6-C30环炔基、C2-C30杂环烷基、卤素(-F、-Cl、-Br、或-I)、醛基(-C(＝O)H)、氨基甲酰基(-C(O)NH 2)、酯基团(-C(＝O)OR，其中R为C1-C6烷基或者C6-C12芳基)，以及其组合。
术语“取代(的)”还可以指其中其氢原子的至少一个被选自如下的取代基代替的化合物、基团或部分：羟基(-OH)、氨基(-NRR′，其中R和R′独立地为氢或C1-C6烷基)、硫醇基团(-SH)、羧酸基团(-COOH)或其盐(-C(＝O)OM，其中M为有机或无机阳离子)、磺酸基团(-SO 3H)或其盐(-SO 3M，其中M为有机或无机阳离子)、磷酸基团(-PO 3H 2)或其盐(-PO 3MH或-PO 3M 2，其中M为有机或无机阳离子)、及其组合。
本领域的技术人员熟知这些取代基的取代方式、取代基的数量，以确保第二基团与非极性有机溶剂的亲和性。
在一个更优选的实施例中，第一配体为油酸或油胺。
在一个实施中，非极性有机溶剂为甲苯或液态烷烃。
在一个实施例中，以质量计，量子点复合物的含量为1.2％-3.6％、第一配体的含量为2％-4％，余量为所述非极性有机溶剂。通常认为，第一配体的量越多， 越有利于量子点复合物在非极性溶剂中的溶解。然而，发明人意外发现，在本申请的方案中，第一配体在量子点复合物分散体系中的含量与量子点复合物在分散体系中的溶解性并不是线性关系。当以质量计，量子点复合物的含量为1.2％-3.6％，第一配体的含量小于2％时，会有部分量子点复合物不能溶解；而当第一配体的含量大于4％时，又会有部分量子点复合物析出。而当以质量计，量子点复合物的含量为1.2％-3.6％、第一配体的含量为2％-4％，余量为所述非极性有机溶剂时，量子点复合物能稳定地溶解在非极性溶剂中，从而形成稳定的量子点复合物分散体系。
在一个实施例中，量子点的表面还连接有第二配体，包覆层覆盖了第二配体。在一个实施例中，第二配体为油酸、油胺、硫醇、三辛基氧膦、三辛基膦中的一种或多种。对于已合成的量子点复合物而言，通常其表面连接有配体(等同于本申请中的第二配体)，以使得量子点复合物能够稳定地分散或溶解在溶剂中。在本申请的方案中，即使存在第二配体，也不会不良地影响包覆层和第一配体，由此极大地简化了本申请的量子点复合物分散体系的制备。
与现有技术相比，本申请的优点在于：(1)本申请的由金属元素、氢元素、氧元素三种成分组成的包覆物在光致发光环境中具有良好的稳定性，这对量子点起到良好的保护作用，使得量子点复合物的稳定性较好，具有较长的寿命，并且包覆物不会不良地影响量子点的光致发光性能，这样量子点复合物不但具有较长的寿命，而且出光强度随时间的延长衰减很小。(2)量子点复合物的包覆层能对量子点复合物起到保护作用，而第一配体具有与非极性有机溶剂亲和的第二基团，这样量子点复合物不但具有良好的稳定性，而且能溶于常见的非极性有机溶剂，从而可以良好地使用这种量子点复合物。
附图说明
图1是样品1的TEM照片；
图2是样品2的TEM照片；
图3是样品3的TEM照片；
图4是样品4的TEM照片；
图5是样品5的TEM照片；
图6是样品6的TEM照片。
图7a是实施例7的样品的TEM照片；
图7b是实施例7的量子点复合物在溶解前和溶解后的发射光谱；
图8a是实施例8的样品的TEM照片；
图8b是实施例8的量子点复合物在溶解前和溶解后的发射光谱；
图9a是实施例9的样品的TEM照片；
图9b是实施例9的量子点复合物在溶解前和溶解后的发射光谱；
图10a是实施例10的样品的TEM照片；以及
图10b是实施例10的量子点复合物在溶解前和溶解后的发射光谱。
具体实施方式
下面将结合本申请实施方式，对本申请的技术方案进行详细地描述。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。
实施例1：
配制异丙醇铝的环己烷溶液形成第二体系，浓度为0.2g/ml。配制红光CdSe的甲苯溶液，浓度为2mg/ml。
取第二体系5ml，取CdSe的甲苯溶液100ml，然后将第二体系加入到CdSe的甲苯溶液中形成第一体系。接下来，向第一体系中通入湿度为40％的氩气，反应得到量子点复合物的样品1，TEM照片如图1所示。在图1中，深色的部分12、13、15是量子点，浅色的部分11、14是包覆物。从图1中可看到，两个量子点12、13被包覆在一起，量子点15是单独被包覆的。
使用杭州科兴光电有限公司生产的CL-200FZ光源光电性能综合测试系统对样品1的出光强度进行了测试。测试条件为：测试系统的工作电流为20mA，激发波长为460nm。将每一预定时刻得到的出光强度值与初始时刻(即，0小时时)的出光强度值相比，得到的结果如表1所示。
实施例2：
配制异丙醇铝的己烷溶液形成第二体系，浓度为0.18g/ml。配制红光CdZnSe的甲苯溶液，浓度为1mg/ml。
取第二体系5ml，取CdZnSe的甲苯溶液120ml，然后将第二体系加入到CdZnSe的甲苯溶液中形成第一体系。接下来，向第一体系中通入湿度为38％的氩气，反应得到量子点复合物的样品2，TEM照片如图2所示。在图2中，深色的部分21、24是量子点，浅色的部分22、23是包覆物。从图2中可看到，量子点21、24是单独被包覆的。
对样品2的出光强度进行了测试，结果如表1所示。测试方式和条件与实施例1相同。
实施例3：
配制仲丁醇铝的戊烷溶液形成第二体系，浓度为0.25g/ml。配制红光InP的正庚烷溶液，浓度为5mg/ml。
取第二体系3ml，取InP的正庚烷溶液85ml，然后将第二体系加入到InP的正庚烷溶液中形成第一体系。接下来，向第一体系中通入湿度为33％的氩气，反应得到量子点复合物的样品3，TEM照片如图3所示。在图3中，深色的部分31、34是量子点，浅色的部分32、33是包覆物。从图3中可看到，量子点31、34是单独被包覆的。
对样品3的出光强度进行了测试，结果如表1所示。测试方式和条件与实施例1相同。
实施例4：
配制叔丁醇钛的辛烷溶液形成第二体系，浓度为0.3g/ml。配制红光CdSe/ZnS的环己烷溶液，浓度为8mg/ml。
取第二体系3ml，取CdSe/ZnS的正己烷溶液190ml，然后将第二体系加入到CdSe/ZnS的环己烷溶液中形成第一体系。接下来，向第一体系中通入湿度为42％的氮气，反应得到量子点复合物的样品4，TEM照片如图4所示。在图4中，深色的部分41、44是量子点，浅色的部分42、43是包覆物。从图4中可看到，量子点41、44是单独被包覆的。
对样品4的出光强度进行了测试，结果如表1所示。测试方式和条件与实施例1相同。
实施例5：
配制异丙醇钛的辛烷溶液形成第二体系，浓度为0.15g/ml。配制红光InP的环辛烷溶液，浓度为10mg/ml。
取第二体系6ml，取InP的正己烷溶液150ml，然后将第二体系加入到InP的环辛烷溶液中形成第一体系。接下来，向第一体系中通入湿度为48％的氮气，反应得到量子点复合物的样品5，TEM照片如图5所示。在图5中，深色的部分52、54、55、56是量子点，浅色的部分51、53是包覆物。从图5中可看到，三个量子点54、55、56被包覆在一起，量子点52是单独被包覆的。
对样品5的出光强度进行了测试，结果如表1所示。测试方式和条件与实施例1相同。
实施例6：
配制异丙醇钛和叔丁醇铝的辛烷溶液形成第二体系，异丙醇钛和叔丁醇铝的合计浓度为0.2g/ml。配制红光InP的环辛烷溶液，浓度为10mg/ml。
取第二体系8ml，取InP的正己烷溶液160ml，然后将第二体系加入到InP的环辛烷溶液中形成第一体系。接下来，向第一体系中通入湿度为44％的氮气，反应得到量子点复合物的样品6，TEM照片如图6所示。在图6中，深色的部分61、63是量子点，浅色的部分62、64是包覆物。从图6中可看到，量子点61、63是单独被包覆的。
对样品6的出光强度进行了测试，结果如表1所示。测试方式和条件与实施例1相同。
对比例1：
使用无包覆物的红光InP量子点作为对比样品1，对对比样品1的出光强度进行了测试，结果如表1所示。测试方式和条件与实施例1相同。
对比例2：
使用无包覆物的红光CdSe/ZnS量子点作为对比样品2，对对比样品2的出光 强度进行了测试，结果如表1所示。测试方式和条件与实施例1相同。
表1
Figure PCTCN2018080189-appb-000001
通常而言，随着测试时间的延长，样品的出光强度相对于初始出光强度会逐渐变化。由表1可知：由本发明的量子点复合物在经过长时间照射激发后，出光强度仍然大于或等于初始出光强度。例如，在经500小时的蓝光照射后，出光强度仍然至少为100％。与现有技术中无包覆的量子点相比，出光强度得到了极大地提高。这说明本发明的量子点复合物具有较长的寿命和良好的光致发光性能。
实施例7：
选取120mg量子点复合物CdSe/Al(OH) 3，即，量子点为CdSe，包覆层为Al(OH) 3。第二配体为油酸。非极性有机溶剂为甲苯，体积5ml。将量子点复合物和甲苯混合，形成第一混合体系。此时，量子点复合物在甲苯中以沉淀物形式存在。
向第一混合体系中加入200μL油酸，量子点复合物溶解形成稳定的量子点复合物分散体系。对量子点复合物分散体系中的量子点复合物拍摄了TEM照片，如图7a。在图7a中，深色部分71为量子点复合物的量子点，浅色部分72为包 覆层Al(OH) 3。
还使用荧光光谱仪测试了量子点复合物在溶解前和溶解后的发射光谱(即，PL)，如图7b。在图7b中，曲线73是量子点复合物在溶解之前的发射光谱，曲线74是量子点复合物在溶解之后的发射光谱。从图7b可得知，在量子点复合物在溶解前和溶解后，发射光谱几乎没有变化，从而有助于量子点复合物的使用。
实施例8：
选取72mg量子点复合物InP/Al(OH) 3，即，量子点为InP，包覆层为Al(OH) 3。第二配体为正十二硫醇。非极性有机溶剂为正辛烷，体积6ml。将量子点复合物和正辛烷混合，形成第一混合体系。此时，量子点复合物在正辛烷中以沉淀物形式存在。
向第一混合体系中加入120μL油酸，量子点复合物溶解形成稳定的量子点复合物分散体系。对量子点复合物分散体系中的量子点复合物拍摄了TEM照片，如图8a。在图8a中，深色部分81为量子点复合物的量子点，浅色部分82为包覆层Al(OH) 3。
还使用荧光光谱仪测试了量子点复合物在溶解前和溶解后的发射光谱(即，PL)，如图8b。在图8b中，曲线83是量子点复合物在溶解之前的发射光谱，曲线84是量子点复合物在溶解之后的发射光谱。从图8b可得知，在量子点复合物在溶解前和溶解后，发射光谱几乎没有变化，从而有助于量子点复合物的使用。
实施例9：
选取48mg量子点复合物CdS/Al(OH) 3，即，量子点为CdS，包覆层为Al(OH) 3。第二配体为油胺。非极性有机溶剂为氯仿，体积4ml。将量子点复合物和氯仿混合，形成第一混合体系。此时，量子点复合物在氯仿中以沉淀物形式存在。
向第一混合体系中加入80μL油胺，量子点复合物溶解形成稳定的量子点复合物分散体系。对量子点复合物分散体系中的量子点复合物拍摄了TEM照片，如图9a。在图9a中，深色部分91为量子点复合物的量子点，浅色部分92为包覆层Al(OH) 3。
还使用荧光光谱仪测试了量子点复合物在溶解前和溶解后的发射光谱(即， PL)，如图9b。在图9b中，曲线93是量子点复合物在溶解之前的发射光谱，曲线94是量子点复合物在溶解之后的发射光谱。从图9b可得知，在量子点复合物在溶解前和溶解后，发射光谱几乎没有变化，从而有助于量子点复合物的使用。
实施例10：
选取144mg量子点复合物ZnSe/Al(OH) 3，即，量子点为ZnSe，包覆层为Al(OH) 3。第二配体为三辛基氧磷。非极性有机溶剂为正庚烷，体积4ml。将量子点复合物和正庚烷混合，形成第一混合体系。此时，量子点复合物在正庚烷中以沉淀物形式存在。
向第一混合体系中加入160μL油胺，量子点复合物溶解形成稳定的量子点复合物分散体系。对量子点复合物分散体系中的量子点复合物拍摄了TEM照片，如图10a。在图10a中，深色部分101为量子点复合物的量子点，浅色部分102为包覆层Al(OH) 3。
还使用荧光光谱仪测试了量子点复合物在溶解前和溶解后的发射光谱(即，PL)，如图10b。在图10b中，曲线103是量子点复合物在溶解之前的发射光谱，曲线104是量子点复合物在溶解之后的发射光谱。从图10b可得知，在量子点复合物在溶解前和溶解后，发射光谱几乎没有变化，从而有助于量子点复合物的使用。
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 (20)

  1. 一种量子点复合物，其包括量子点和包覆所述量子点的包覆物，所述包覆物由金属元素、氢元素、氧元素三种成分组成并且不溶于水。
  2. 根据权利要求1所述的量子点复合物，其特征在于，所述包覆物为氢氧化铝、氢氧化钛、羟基氧化铝和羟基氧化钛中的一种或多种的混合。
  3. 根据权利要求1或2所述的量子点复合物，其特征在于，被包覆的量子点的数量为一个；
    优选地，所包覆的量子点的数量为两个或更多个；
    更优选地，所述两个或更多个的量子点彼此分开。
  4. 根据权利要求1到3中任一项所述的量子点复合物，其特征在于，在所述包覆物的外表面上无有机物配体。
  5. 根据权利要求1到4中任一项所述的量子点复合物，其特征在于，所述量子点复合物的粒径在15nm到100nm之间；
    优选地，所述包覆物的厚度在2nm到45nm之间。
  6. 一种制备量子点复合物的方法，包括以下步骤，
    步骤1)：将金属醇盐加入到含有量子点的有机溶剂中，形成第一体系，
    步骤2)：向所述第一体系内引入水，
    步骤3)：在所述步骤2)之后，所述第一体系内发生反应生成量子点复合物，
    所述量子点复合物包括量子点和包覆所述量子点的包覆物，所述包覆物由金属元素、氢元素、氧元素三种成分组成并且不溶于水。
  7. 根据权利要求6所述的方法，其特征在于，在所述步骤1)中，首先将金属醇盐溶解在液态烷烃中形成第二体系，然后将所述第二体系加入到所述量子点的有机溶剂中，
    优选地，所述液态烷烃为C5到C13的烷烃，或C5到C8的环烷烃，
    更优选地，所述含有量子点的有机溶剂为甲苯、或C5到C13的烷烃，或C5到C8的环烷烃。
  8. 根据权利要求6或7所述的方法，其特征在于，在所述步骤2)中，将水蒸气与惰性气体的混合气体通入到所述第一体系中，以向所述第一体系内引入水；优选地，含有水蒸气的惰性气体的湿度在33％到48％之间。
  9. 根据权利要求6到8中任一项所述的方法，其特征在于，所述金属醇盐为C3或C4的饱和金属醇盐。
  10. 根据权利要求9所述的方法，其特征在于，所述金属醇盐为异丙醇铝、仲丁醇铝、异丙醇钛和叔丁醇钛中的一种或多种的混合。
  11. 量子点复合物分散体系，包括：非极性有机溶剂，和分散在所述非极性有机溶剂中的量子点复合物，
    所述量子点复合物包括量子点和包覆所述量子点的包覆物，所述包覆物由金属元素、氢元素、氧元素三种成分组成并且不溶于水、连接在所述包覆物上的第一配体，
    所述第一配体具有与所述包覆物相连的第一基团和与所述非极性有机溶剂亲和的第二基团。
  12. 根据权利要求11所述的量子点复合物分散体系，其特征在于，所述包覆物为氢氧化铝、氢氧化钛、羟基氧化铝和羟基氧化钛中的一种或多种的混合。
  13. 根据权利要求12所述的量子点复合物分散体系，其特征在于，所述第一基团为羧基或氨基。
  14. 根据权利要求12或13所述的量子点复合物分散体系，其特征在于，所述第二基团为C6-C22的脂肪族烃基。
  15. 根据权利要求14所述的量子点复合物分散体系，其特征在于，所述脂肪族烃基上还具有取代基团，
    所述取代基团为取代或不取代的C4-C22的脂环族烃基，和/或取代或不取代的C6-C22的芳香族烃基。
  16. 根据权利要求12到15中任一项所述的量子点复合物分散体系，其特征在于，所述第一配体为油酸或油胺。
  17. 根据权利要求11到16中任一项所述的量子点复合物分散体系，其特征在于，所述非极性有机溶剂为甲苯、氯仿或液态烷烃。
  18. 根据权利要求11到17中任一项所述的量子点复合物分散体系，其特征在于，以质量计，所述量子点复合物的含量为1.2％-3.6％、所述第一配体的含量为2％-4％，余量为所述非极性有机溶剂。
  19. 根据权利要求11到18中任一项所述的量子点复合物分散体系，其特征在于，所述量子点的表面还连接有第二配体，所述包覆物覆盖了所述第二配体。
  20. 根据权利要求19所述的量子点复合物分散体系，其特征在于，所述第二配体为油酸、油胺、硫醇、三辛基氧膦、三辛基膦中的一种或多种。
PCT/CN2018/080189 2018-02-22 2018-03-23 量子点复合物、其制备方法和量子点复合物分散体系 WO2019161588A1 (zh)

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