CN110591691B - Metal oxide coated quantum dot and preparation method thereof - Google Patents
Metal oxide coated quantum dot and preparation method thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 124
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 85
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims description 78
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000005303 weighing Methods 0.000 claims description 24
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 22
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 22
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000005642 Oleic acid Substances 0.000 claims description 22
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 22
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 22
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012702 metal oxide precursor Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkyl mercaptan Chemical compound 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 9
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- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
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Abstract
The invention relates to the technical field of quantum dot optical materials, in particular to a metal oxide coated quantum dot and a preparation method thereof. In the quantum dot coated with the metal oxide, the quantum dot core comprises at least three layers of metal oxides, and the refractive index of the metal oxide layers is gradually increased or equal from the inner layer to the outer layer. The quantum dots are coated by the multilayer metal oxide, so that the oxidation resistance of the quantum dots is improved; and the refractive index of the metal oxide layer is gradually increased or equal from the inner layer to the outer layer, so that the good light transmission is still kept even under the cladding of multiple layers of metals, and the loss of exciting light entering the quantum dots is avoided. In the preparation method, the quantum dots coated with the metal oxide are synthesized by adopting a one-pot method, the quantum dots coated with the metal oxide are synthesized in the same reaction system, the reaction liquid does not need to be transferred or purified, the production efficiency is high, the reaction system is always under the protection of nitrogen, and the quantum dots can not be damaged by oxygen before the coating of the metal oxide is finished.
Description
Technical Field
The invention relates to the technical field of quantum dot optical materials, in particular to a metal oxide coated quantum dot and a preparation method thereof.
Background
The quantum dots have small particle size, large specific surface area and high surface energy, and are easily oxidized in application, so that fluorescence is quenched.
Coating the surface of the quantum dot with a metal oxide is a common method for improving the oxidation resistance of the quantum dot. Quantum dot preparation methods as disclosed in patent applications CN201710199967, CN201710301382, CN201810713517, CN201610217470.2, however common to these methods are: the metal precursor is added to the quantum dot solution or dispersion to react to obtain the metal oxide layer. The synthesis of the quantum dots and the coating of the metal oxide are two independent reaction processes, and the quantum dots are firstly synthesized and extracted from the reaction liquid, so that the coating process of the metal oxide can be further completed.
The scheme has the disadvantages that the step (1) is more in aggregation, the time is longer, and the production efficiency is lower; (2) After the quantum dots are extracted from the anhydrous and oxygen-free reaction liquid and before the quantum dots are coated with the metal oxide, the quantum dots are not protected by the metal oxide, are easy to oxidize, and the fluorescence can be attenuated; (3) Only one layer of metal oxide has insufficient oxidation resistance.
Patent CN201910245760, published as 2019, 06, 25, discloses a quantum dot and a preparation method thereof, and the specific method is to complete synthesis of the quantum dot and coating of metal oxide in the same reaction system, wherein the outer layer of the quantum dot is a structure with quantum dot shell layers/metal oxide layers arranged alternately. However, the quantum structure provided by the invention has the problem of low utilization rate of exciting light; the inventor finds out the reason that the structure has low utilization rate of exciting light in many years of research, and the quantum dot shell layer in the technical scheme is any one of ZnS, znSe, znTe and ZnSeS, and the resolution ratios are about 2.3, 2.5, 3 and 2.4 respectively; the metal oxide used is ZnO, the resolution ratio is about 1.9; because the difference between the refractive indexes of the quantum dot shell and the metal oxide is large, when excitation light enters a medium with a low refractive index from a medium with a high refractive index, total reflection is easy to occur, so that the excitation light entering the quantum dot is lost on the interface between the quantum dot shell and the metal oxide. The structure of the invention has a plurality of interfaces, which remarkably reduces the utilization rate of exciting light and causes the loss of the luminous brightness of the product.
Disclosure of Invention
In order to solve the problems mentioned in the background art, the present invention provides a metal oxide coated quantum dot, wherein the quantum dot core comprises at least three layers of metal oxides, and the refractive index of the metal oxide layers is gradually increased or equal from an inner layer to an outer layer.
On the basis of the scheme, the quantum dot core is CdZnSe/ZnS (core/shell).
On the basis of the scheme, further, the metal oxide comprises ZnO and ZrO 2 、Al 2 O 3 、MgO、NiO、In 2 O 3 Any one of the above;
wherein the ZnO refractive index is 1.9 2 Has a refractive index of 2.1,Al 2 O 3 Has a refractive index of 1.61-1.63, a refractive index of MgO of 1.73-1.75, a refractive index of NiO of 2.1, in 2 O 3 Has a refractive index of 2.05.
The invention also provides a preparation method of the metal oxide coated quantum dot, which comprises the following steps:
step a, preparing a solution containing quantum dot cores in a quantum dot core precursor solution;
b, adding long-chain mercaptan into the solution containing the quantum dot core to coat the quantum dot core with the quantum dot shell;
c, adding a metal oxide precursor and alkyl alcohol into the quantum dot core solution coated with the quantum dot shell to coat the metal oxide on the surface of the quantum dot shell; repeating the steps to coat the multiple layers of metal oxides;
and d, adding toluene and ethanol into the solution coated with the metal oxide, uniformly mixing, centrifuging, and drying the obtained precipitate to obtain the quantum dot coated with the metal oxide.
On the basis of the scheme, further, in the step a, a Zn precursor is placed in a container, in a protective gas, the temperature is raised to 300 ℃, a Cd precursor is injected into a reaction liquid, after the reaction, a Se precursor is injected into the reaction liquid for reaction, and the temperature is lowered to 200-250 ℃ to obtain a quantum dot core;
in the step b, adding alkyl mercaptan into the solution containing the quantum dot core at 200-250 ℃, and reacting for 30-60min to form a ZnS shell structure;
in step c, the reaction temperature is 200-250 ℃.
On the basis of the scheme, in the step b, further, the alkyl mercaptan comprises any one of octyl mercaptan, dodecyl mercaptan, tetradecyl mercaptan and octadecyl mercaptan.
On the basis of the scheme, the preparation method of the Zn precursor comprises the following steps: weighing zinc acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a Zn precursor solution;
the preparation method of the Cd precursor comprises the following steps: weighing cadmium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃, and obtaining a Zn precursor solution;
the preparation method of the Se precursor comprises the following steps: weighing selenium powder in a container, adding tributyl phosphine, and performing ultrasonic dissolution to obtain Se precursor solution.
On the basis of the scheme, in the step c, the alkyl alcohol is any one of octanol and dodecanol.
On the basis of the scheme, the metal oxides ZnO and ZrO 2 、Al 2 O 3 、MgO、NiO、In 2 O 3 Any one of the above;
wherein,
the preparation method of the zinc oxide precursor comprises the following steps: weighing zinc acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a Zn precursor solution;
the preparation method of the zirconium oxide precursor comprises the following steps: weighing zirconium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a zirconium oxide precursor;
the preparation method of the aluminum oxide precursor comprises the following steps: weighing aluminum acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃, and obtaining an aluminum oxide precursor;
the preparation method of the magnesium oxide precursor comprises the following steps: weighing magnesium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃, and obtaining a magnesium oxide precursor;
the preparation method of the nickel oxide precursor comprises the following steps: weighing nickel acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a nickel oxide precursor;
the preparation method of the indium oxide precursor comprises the following steps: weighing indium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain an indium oxide precursor.
According to the quantum dot coated with the metal oxide, the quantum dot is coated with the multiple layers of metal oxides, so that the oxidation resistance of the quantum dot is improved; and the refractive index of the metal oxide layer is gradually increased or equal from the inner layer to the outer layer, so that the good light transmission is still kept even under the cladding of multiple layers of metals, and the loss of exciting light entering the quantum dots is avoided.
In the preparation method provided by the invention, the quantum dots coated with the metal oxide are synthesized by adopting a one-pot method, the quantum dots coated with the metal oxide are synthesized in the same reaction system, reaction liquid does not need to be transferred or purified in the process, the number of steps is small, the production efficiency is high, the reaction system is always under the protection of nitrogen, and the quantum dots cannot be damaged by oxygen before the coating of the metal oxide is finished.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a transmission electron microscope test result diagram of quantum dots before being coated with metal oxide in example 1 provided by the present invention;
fig. 2 is a transmission electron microscope test result diagram of quantum dots coated with metal oxide in example 1 provided by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention provides the following examples of metal oxide coated quantum dots
Example 1
The quantum dots are CdZnSe/ZnS (core/shell), the metal oxide layer is three layers, and ZnO and In are sequentially arranged from the inner layer to the outer layer 2 O 3 And ZrO 2 。
Example 2
The quantum dots are CdZnSe/ZnS (core/shell), the metal oxide layer is three layers, and Al is arranged from the inner layer to the outer layer in sequence 2 O 3 MgO and NiO.
Example 3
The quantum dots are CdZnSe/ZnS (core/shell), the metal oxide layer is three layers, and Al is arranged from the inner layer to the outer layer in sequence 2 O 3 、ZnO、ZrO 2 。
Example 4
The quantum dots are CdZnSe/ZnS (core/shell), the metal oxide layer is four layers, and MgO, znO and ZrO are arranged from the inner layer to the outer layer in sequence 2 、NiO。
The invention provides the following embodiments of a preparation method of metal oxide coated quantum dots:
example A
Step a, preparing a solution containing quantum dot cores in a quantum dot core precursor solution:
measuring 30mL of Zn precursor in a flask, heating to 300 ℃ under the protection of nitrogen and stirring, injecting 1.5mL of Cd precursor into a reaction solution, injecting 1mL of Se precursor into the reaction solution after reacting for 5min, cooling to 250 ℃ after reacting for 30min, and obtaining a quantum dot core;
and step b, slowly dropwise adding 4mL of octyl mercaptan into the reaction liquid containing the quantum dot core at 250 ℃, and reacting for 60min to form a ZnS shell structure.
Step c, adding 2mL of aluminum oxide precursor into the reaction liquid containing the quantum dots at 220 ℃, then slowly dropwise adding dodecanol, and reacting for 40min to form a metal oxide layer structure;
repeating the steps, and sequentially replacing the metal oxide precursor with a zinc oxide precursor and a zirconium oxide precursor to obtain the multilayer metal oxide layer structure.
Example B
Step a, preparing a solution containing quantum dot cores in a quantum dot core precursor solution:
measuring 30mL of Zn precursor in a flask, heating to 300 ℃ under the protection of nitrogen and stirring, injecting 1.2mL of Cd precursor into a reaction solution, reacting for 5min, injecting 0.8mL of Se precursor into the reaction solution, reacting for 20min, and cooling to 220 ℃ to obtain quantum dot nuclei;
and step b, slowly dropwise adding 3mL of dodecyl mercaptan into the reaction liquid containing the quantum dot core at 220 ℃, and reacting for 40min to form a ZnS shell structure.
C, adding 1.5mL of aluminum oxide precursor into the reaction liquid containing the quantum dots at 220 ℃, then slowly dripping octanol, and reacting for 40min to form a metal oxide layer structure;
repeating the steps, and sequentially replacing the metal oxide precursor with a magnesium oxide precursor and a nickel oxide precursor to obtain the multilayer metal oxide layer structure.
Example C
Step a, preparing a solution containing quantum dot cores in a quantum dot core precursor solution:
measuring 30mL of Zn precursor in a flask, heating to 300 ℃ under the protection of nitrogen and stirring, injecting 1.0mL of Cd precursor into a reaction solution, reacting for 5min, injecting 0.7mL of Se precursor into the reaction solution, reacting for 15min, and cooling to 200 ℃ to obtain a quantum dot core;
and step b, slowly dropwise adding 3mL of tetradecylthiol into the reaction liquid containing the quantum dot core at 200 ℃, and reacting for 30min to form a ZnS shell structure.
C, adding 1.5mL of aluminum oxide precursor into the reaction liquid containing the quantum dots at 200 ℃, then slowly dripping octanol, and reacting for 40min to form a metal oxide layer structure;
repeating the steps, and sequentially replacing the metal oxide precursor with a magnesium oxide precursor and a nickel oxide precursor to obtain the multilayer metal oxide layer structure.
Examples of the above preparation methods:
the preparation method of the zinc oxide precursor comprises the following steps: weighing 30mmol of zinc acetate in a container, adding 40mL of oleic acid and 20mL of octadecene, vacuumizing and heating to 160 ℃, and obtaining a Zn precursor solution;
the preparation method of the zirconium oxide precursor comprises the following steps: weighing 30mmol of zirconium acetate in a container, adding 40mL of oleic acid and 20mL of octadecene, vacuumizing and heating to 160 ℃ to obtain a zirconium oxide precursor;
the preparation method of the aluminum oxide precursor comprises the following steps: weighing 30mmol of aluminum acetate in a container, adding 40mL of oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain an aluminum oxide precursor;
the preparation method of the magnesium oxide precursor comprises the following steps: weighing 30mL of magnesium acetate in a container, adding 40mL of oleic acid and 20mL of octadecene, vacuumizing and heating to 160 ℃ to obtain a magnesium oxide precursor;
the preparation method of the nickel oxide precursor comprises the following steps: weighing 30mL of nickel acetate in a container, adding 40mL of oleic acid and 20mL of octadecene, vacuumizing and heating to 160 ℃ to obtain a nickel oxide precursor;
the preparation method of the indium oxide precursor comprises the following steps: weighing 30mL of indium acetate in a container, adding 40mL of oleic acid and 20mL of octadecene, vacuumizing and heating to 160 ℃ to obtain an indium oxide precursor.
In the embodiment 1 of the invention, the quantum dots before being coated with the metal oxide are subjected to a transmission electron microscope test, as shown in fig. 1; the quantum dots coated with the metal oxide were subjected to transmission electron microscopy as shown in fig. 2. As can be seen from fig. 1 and 2, the particle size of the coated quantum dots is increased by comparing the particle sizes of the quantum dots before and after coating, and a distinct metal oxide layer is visible on the outer layer of the quantum dots, which indicates that the synthesis method of the present invention can coat the quantum dots with the metal oxide.
In addition, the invention also provides the following comparative examples of metal oxide coated quantum dots:
comparative example 1: the quantum dots are CdZnSe/ZnS (core/shell), the metal oxide layer is three layers, and ZrO is arranged from the inner layer to the outer layer in sequence 2 、In 2 O 3 And ZnO.
Comparative example 2: the quantum dots are CdZnSe/ZnS (core/shell), the metal oxide layer is three layers, and Al is arranged from the inner layer to the outer layer in sequence 2 O 3 NiO and MgO.
Comparative example 3: the quantum dots are CdZnSe/ZnS (core/shell), the metal oxide layer is three layers, and ZnO and Al are sequentially arranged from the inner layer to the outer layer 2 O 3 And ZrO 2 。
The metal oxide coated quantum dots prepared in examples 1 to 3 of the present invention and comparative examples 1 to 3 were subjected to the following tests:
the test method comprises the following steps: the quantum dot film is prepared by uniformly mixing quantum dot and film-forming glue, the color coordinates of quantum dot films prepared by adopting different quantum dots are close by adjusting the proportion of the quantum dot to the glue, the deviation of the x value is less than 0.004, the deviation of the y value is less than 0.004, and the brightness of the quantum dot films of different samples is detected, wherein the detection results are shown in the following table:
TABLE 1
As can be seen from the above comparison, the quantum dot films prepared from the samples provided in comparative examples 1 to 3 have brightness significantly lower than that of the quantum dot films prepared from the samples provided in examples 1 to 3 of the present patent application, using the same material but without considering the refractive index factors of the different metal oxide clad layers.
In the process of years of research, the inventor of the patent application discovers the reason of light loss in the quantum dots coated by the multilayer metal oxide for the first time, and proposes a technical scheme that the quantum dots are coated by the multilayer metal oxide, and the refractive index of the metal oxide layer is gradually increased or equal from the inner layer to the outer layer, so that the quantum dots still maintain good light transmission even under the condition of multilayer metal coating, and the problem of light loss caused by light entering the quantum dots is avoided;
in addition, in the preparation method, the quantum dots coated with the metal oxide are synthesized by adopting a one-pot method, the quantum dots coated with the metal oxide are synthesized in the same reaction system, reaction liquid does not need to be transferred or purified in the process, the number of steps is small, the production efficiency is high, the reaction system is always under the protection of nitrogen, and the quantum dots cannot be damaged by oxygen before the coating of the metal oxide is finished.
The technical scheme provided by the invention provides a valuable reference thought for the improvement of the technical field of the optical quantum dots, and has important practical application prospect.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A metal oxide coated quantum dot, comprising:
three layers of metal oxides are coated outside the quantum dot core, and the quantum dot core is CdZnSe/ZnS; the three layers of metal oxides are ZnO and In sequence from the inner layer to the outer layer 2 O 3 、ZrO 2 ；
Or the three layers of metal oxides are sequentially Al from the inner layer to the outer layer 2 O 3 、MgO、NiO；
Or the three layers of metal oxides are sequentially Al from the inner layer to the outer layer 2 O 3 、ZnO、ZrO 2 。
2. The method for preparing the metal oxide coated quantum dot according to claim 1, comprising the following steps:
step a, preparing a solution containing quantum dot cores in a quantum dot core precursor solution;
b, adding long-chain mercaptan into the solution containing the quantum dot core to coat the quantum dot core with the quantum dot shell;
c, adding a metal oxide precursor and alkyl alcohol into the obtained quantum dot core solution coated with the quantum dot shell to coat the metal oxide on the surface of the quantum dot shell; repeating the steps to coat the multiple layers of metal oxides;
and d, adding toluene and ethanol into the solution coated with the metal oxide, uniformly mixing, centrifuging, and drying the obtained precipitate to obtain the quantum dot coated with the metal oxide.
3. The method for preparing a metal oxide coated quantum dot according to claim 2, wherein:
step a, putting a Zn precursor into a container, heating to 300 ℃ in a protective gas, injecting a Cd precursor into a reaction liquid, after reaction, injecting a Se precursor into the reaction liquid for reaction, and cooling to 200-250 ℃ to obtain a quantum dot core;
in the step b, adding alkyl mercaptan into the solution containing the quantum dot core at 200-250 ℃, and reacting for 30-60min to form a ZnS shell structure;
in step c, the reaction temperature is 200-250 ℃.
4. The method for preparing the metal oxide coated quantum dot according to claim 3, wherein:
in step b, the alkyl mercaptan is selected from any one of octyl mercaptan, dodecyl mercaptan, tetradecyl mercaptan and octadecyl mercaptan.
5. The method for preparing the metal oxide coated quantum dot according to claim 3, wherein:
the preparation method of the Zn precursor comprises the following steps: weighing zinc acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a Zn precursor solution;
the preparation method of the Cd precursor comprises the following steps: weighing cadmium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃, and obtaining a Zn precursor solution;
the preparation method of the Se precursor comprises the following steps: weighing selenium powder in a container, adding tributyl phosphine, and performing ultrasonic dissolution to obtain Se precursor solution.
6. The method for preparing a metal oxide coated quantum dot according to claim 2, wherein:
in the step c, the alkyl alcohol is any one of octanol and dodecanol.
7. The method for preparing a metal oxide coated quantum dot according to claim 2, wherein:
the preparation method of the zinc oxide precursor comprises the following steps: weighing zinc acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a Zn precursor solution;
the preparation method of the zirconium oxide precursor comprises the following steps: weighing zirconium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a zirconium oxide precursor;
the preparation method of the aluminum oxide precursor comprises the following steps: weighing aluminum acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃, and obtaining an aluminum oxide precursor;
the preparation method of the magnesium oxide precursor comprises the following steps: weighing magnesium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a magnesium oxide precursor;
the preparation method of the nickel oxide precursor comprises the following steps: weighing nickel acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain a nickel oxide precursor;
the preparation method of the indium oxide precursor comprises the following steps: weighing indium acetate in a container, adding oleic acid and octadecene, vacuumizing and heating to 160 ℃ to obtain an indium oxide precursor.
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