CN116120930A - Preparation method for improving size uniformity of quantum dots and quantum dots - Google Patents
Preparation method for improving size uniformity of quantum dots and quantum dots Download PDFInfo
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 22
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 15
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- 239000012682 cationic precursor Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012683 anionic precursor Substances 0.000 claims description 5
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- 239000012769 display material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
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- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000012356 Product development Methods 0.000 description 1
- ZTSAVNXIUHXYOY-CVBJKYQLSA-L cadmium(2+);(z)-octadec-9-enoate Chemical compound [Cd+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O ZTSAVNXIUHXYOY-CVBJKYQLSA-L 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000010899 nucleation Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- MJNSMKHQBIVKHV-UHFFFAOYSA-N selenium;trioctylphosphane Chemical compound [Se].CCCCCCCCP(CCCCCCCC)CCCCCCCC MJNSMKHQBIVKHV-UHFFFAOYSA-N 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/661—Chalcogenides
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- 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
Abstract
The invention discloses a preparation method for improving size uniformity of quantum dots and the quantum dots, and relates to the technical field of quantum dot display materials. The preparation method comprises the following steps: vacuumizing a cation precursor, heating to a first reaction temperature, reacting an anion precursor with the cation precursor to form a first mixture comprising binary phase clusters and short-wave binary phase quantum dots, and cooling to a first termination reaction temperature; vacuumizing the first organic solvent, heating to a second reaction temperature, injecting the first mixture into the first organic solvent to react to form a second mixture comprising residual clusters and long-wave binary phase quantum dots, and cooling to a second termination reaction temperature; mixing and stirring the second mixture and a second organic solvent to form a clear and transparent solution, and cooling to room temperature; and (3) reacting the clear and transparent solution with a nonpolar reagent and a polar reagent to form a turbid liquid, and then separating to obtain the aqueous solution. Which can improve the uniformity of particle size of the quantum dots and increase the particle size.
Description
Technical Field
The invention relates to the technical field of quantum dot display materials, in particular to a preparation method for improving size uniformity of quantum dots and the quantum dots.
Background
The quantum dot display material is praised as the most ideal luminescent material in the 21 st century, and the quantum dot material can be applied to the fields of display, illumination, batteries, biology and the like; a number of quantum dot luminescent materials have been processed into display products to the market.
Quantum dots belong to the field of nano materials, the synthesis of related nano materials has been developed for many years, and the synthesis categories of quantum dot material systems mainly comprise a water phase and an oil phase; the synthesis of the quantum dots by the oil phase method is mainly completed by two main steps of nucleation by a hot injection method and shell growth by a continuous ion layer method.
Aiming at the quantum dots of the oil phase synthesis method, the preparation paths of different systems are different, the luminescent quantum dots of some systems are nucleated by adopting conventional heat injection, and the continuous ion layer growth shell can realize the preparation of the corresponding quantum dots, but the quality of the quantum dot material is not very good, and the luminescent quantum dots mainly show the aspects of poor color purity, low fluorescence quantum yield, poor stability and the like. Part of the reasons for the occurrence of such phenomena are that the problems of poor size uniformity, many surface defects, difficult control and the like caused by the larger difference of the reactivity of anion and cation precursors in the process of preparing the quantum dot core, and no particularly good technical scheme can solve the problems at present, so that a certain limiting effect is generated for the subsequent related application and product development.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method for improving the uniformity of the size of quantum dots, which can improve the uniformity of the particle size of the quantum dots and increase the particle size.
The invention aims to provide a quantum dot which has good particle size uniformity and large particle size.
The invention is realized in the following way:
in a first aspect, the present invention provides a method of preparing for improving the uniformity of the size of quantum dots, comprising:
vacuumizing a cation precursor, heating to a first reaction temperature, and reacting an anion precursor with the cation precursor to form a first mixture, wherein the first mixture comprises binary phase clusters and short-wave binary phase quantum dots; cooling to a first termination reaction temperature;
vacuumizing a first organic solvent, heating to a second reaction temperature, and injecting the first mixture into the first organic solvent to react to form a second mixture, wherein the second mixture comprises residual crystal clusters and long-wave binary phase quantum dots; cooling to a second termination reaction temperature;
mixing and stirring the second mixture and a second organic solvent to form a clear and transparent solution, and then cooling to room temperature;
and (3) reacting the clear and transparent solution with a nonpolar reagent and a polar reagent to form a turbid liquid, and then separating to obtain the aqueous solution.
In a second aspect, the present invention provides a quantum dot prepared by the method of any one of the preceding embodiments, wherein the uniformity of the size of the quantum dot is improved.
The invention has the following beneficial effects:
according to the preparation method for improving the size uniformity of the quantum dots, the first mixture containing binary phase clusters and short-wave binary phase quantum dots is formed through mixed reaction of the cation precursor and the anion precursor, the binary phase clusters can be effectively formed through effectively controlling the reaction time, the reaction temperature and the reaction termination temperature in the process of forming the first mixture, in addition, the binary phase clusters in the first mixture are consumed through the reaction of the high-temperature first organic solvent and the first mixture, and the short-wave binary phase quantum dots are reacted to generate the long-wave binary phase quantum dots, so that the prepared quantum dots are more uniform, and the purity, the fluorescence intensity and the quantum yield of the quantum dots are improved.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an ultraviolet-visible light absorption diagram of InP prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The application provides a preparation method for improving the uniformity of the size of quantum dots, which comprises the following steps:
s1, vacuumizing a cation precursor, heating to a first reaction temperature, reacting an anion precursor with the cation precursor to form a first mixture, and cooling to a first termination reaction temperature.
In this application, cationic precursors include, but are not limited to, zn (OA) 2 、Cd(OA) 2 、Pb(OA) 2 、In 2 (OA) 3 、Cu(OA) 2 、Ag 2 (OA) 2 、Hg(OA) 2 、Zn(MA) 2 、Cd(MA) 2 、Pb(MA) 2 、In 2 (MA) 3 、Cu(MA) 2 、Ag 2 (MA) 2 、Hg(MA) 2 、Zn(PA) 2 、Cd(PA) 2 、Pb(PA) 2 、In 2 (PA) 3 、Cu(PA) 2 、Ag 2 (PA) 2 、Hg(PA) 2 、Zn(LA) 2 、Cd(LA) 2 、Pb(LA) 2 、In 2 (LA) 3 、Cu(LA) 2 、Ag 2 (LA) 2 And Hg (LA) 2 At least one of them. In this application, the cationic precursor may be prepared autonomously, preferably using a cationic oxide and oleic acid to prepare the particular desired cationic precursor of the present application.
The anion precursor comprises S-ODE, S-TOP, S-OA, se-TOP, S-OLA, S-TBP, se-TBP, te-ODE, te-OA, te-TOP, te-TBP, (TMS) 3 S、(TMS) 3 P and (TMS) 3 At least one of As.
Vacuumizing the cation precursor at room temperature, and then heating to the vacuumizing temperature to continue vacuumizing; then converting into normal pressure and introducing protective gas. Preferably, the evacuation temperature is 25℃to 180 ℃. The vacuum pumping temperature can be divided into 25-80 ℃, 25-110 ℃, 25-150 ℃ and 25-180 ℃ according to different reaction systems. After the evacuation is completed, the temperature is raised to a first reaction temperature, which in this application is 80-350 ℃. The first reaction temperature can be divided into 80-110 deg.c, 110-150 deg.c, 150-200 deg.c, 200-250 deg.c, 250-300 deg.c and 300-350 deg.c according to different reaction systems.
The reaction of the anion precursor and the cation precursor may be performed by adding the anion precursor to the cation precursor, or by injecting the cation precursor into the anion precursor, and performing a mixing reaction. In the present application, it is preferable to inject the anion precursor into the cation precursor having the first reaction temperature, and keep the first reaction temperature for 10s to 300s, and the reaction time range may be divided into 10 to 60s,60 to 120s,120s to 300s according to different reaction systems.
The molar ratio of the cationic precursor to the anionic precursor in the method is 1-10:1, and the ratio range can be divided into 1-2:1, 1-4:1, 1-6:1 and 1-10:1 according to different reaction systems. The inventor researches find that the first mixture prepared by adopting the molar ratio to carry out the mixing reaction comprises binary phase clusters and short wave binary phase quantum dots with the same components; the mixing proportion of the binary phase clusters and the binary phase quantum dots is 1-9: 1. preferably, the binary phase quantum dots include, but are not limited to, at least one of CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, cuS.
After the reaction for the above time, the reaction system is cooled to 25 ℃ to 300 ℃ as a first termination reaction temperature, and it is understood that the first termination reaction temperature is lower than the first reaction temperature. The temperature range can be divided into 25-50 ℃, 50-90 ℃, 90-120 ℃, 120-150 ℃, 150-180 ℃, 180-220 ℃, 220-250 ℃, 250-280 ℃ and 280-300 ℃ according to different reaction systems. In the application, the substances in the first mixture do not react at the first termination reaction temperature, so that the first reaction temperature is cooled to the first termination reaction temperature within 25-40min at the speed of 2-4 ℃/min, and the components (binary phase clusters and short-wave binary phase quantum dots) in the first mixture can be effectively controlled, so that the quantum dots with more uniform sizes and larger particle sizes can be conveniently prepared subsequently.
The binary phase crystal cluster is an atomic aggregate formed by anion-cation precursors in a certain temperature range and between single atoms and solid state, and the atomic aggregate can participate in the epitaxial growth of quantum dot nanocrystals; the atomic mass participates in epitaxial crystallization at a slower rate than the separation of the anion and cation precursors as epitaxial raw materials. Therefore, the reaction speed is reduced, the reaction is more stable, and more uniform quantum dots are formed.
In the application, the first mixture containing binary phase clusters and short-wave binary phase quantum dots is formed by utilizing the mixed reaction of the cationic precursor and the anionic precursor, and the binary phase clusters can be effectively formed by effectively controlling the reaction time, the reaction temperature and the reaction termination temperature in the process of forming the first mixture, so that the prepared quantum dots are more uniform, and the purity, the fluorescence intensity and the quantum yield of the quantum dots are improved.
S2, vacuumizing the first organic solvent, heating to a second reaction temperature, injecting the first mixture into the first organic solvent to react to form a second mixture, and cooling to the second reaction termination temperature;
in the application, the first organic solvent is vacuumized at room temperature, then heated to a vacuumizing temperature (25-180 ℃ C., which can be divided into 25-80 ℃ C., 25-110 ℃ C., 25-150 ℃ C., 25-180 ℃ C., according to different reaction systems), continuously vacuumized, then converted into normal pressure and introduced with protective gas. Then heating to a second reaction temperature (110-350 ℃, the second reaction temperature can be divided into 110-150 ℃, 150-180 ℃, 180-210 ℃, 210-250 ℃ and 250-300 ℃ according to different reaction systems), then maintaining the temperature and rapidly injecting the first mixture into the first organic solvent, wherein in the injection process, the first organic solvent is in an excessive state and has a certain temperature, so that binary phase clusters and short-wave binary phase quantum dots in the first mixture react with the first organic solvent, and the formed second mixture comprises residual clusters and long-wave binary phase quantum dots; preferably, the proportion of residual clusters in the second mixture after the reaction is finished is less than 5%. After the reaction forms a second mixture, the second reaction temperature is cooled to a second termination reaction temperature (80-180 ℃) within 25-60min at a speed of 2-4 ℃/min, and the substances in the second mixture do not continue to react at the second termination reaction temperature, wherein the first termination reaction temperature is lower than the first reaction temperature. By controlling the cooling speed, the method is beneficial to controlling the size uniformity of the quantum dots and improving the stability of the quantum dots.
Wherein the first organic solvent includes, but is not limited to, at least one of octadecene, paraffin oil, and paraffin oil; preferably, the volume ratio of the first organic solvent to the first mixture is 5 to 30:1.
s3, mixing and stirring the second mixture and the second organic solvent to form a clear and transparent solution, and cooling to room temperature;
preferably, the second organic solvent includes, but is not limited to, at least one of trioctylphosphine, tributylphosphine, trioctylamine, oleylamine, and oleic acid;
preferably, the volume ratio of the second organic solvent to the second mixture is 1: 4-20;
preferably, the reaction time of the second organic solvent and the second mixture is 5-60 min;
s4, reacting the clear and transparent solution with a nonpolar reagent and a polar reagent to form a turbid liquid, and then separating to obtain the aqueous solution.
In the application, the quantum dots are washed by using a nonpolar reagent and a polar reagent, wherein the nonpolar reagent comprises at least one of toluene, chloroform, n-hexane and n-heptane; polar agents include, but are not limited to, at least one of ethanol, methanol, butanol, and isopropanol.
Preferably, the volume ratio of the non-polar agent to the second mixture is (1-5): 10; the volume ratio of the polar reagent to the second mixture is (5-15): 10.
in a second aspect, the present invention provides a quantum dot prepared by the method of any one of the preceding embodiments, wherein the uniformity of the size of the quantum dot is improved.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1: provides an InP QD
1) indium/In oleate 2 (OA) 3 Is prepared from the following steps:
1mmol of InCl is taken 3 And 3ml of Oleic Acid (OA) are added into a 50ml three-neck flask, vacuumizing is carried out for 10min at low temperature, then the mixed solution is heated to 110 ℃ and vacuumized for 2h, after vacuumizing, the mixed solution is converted into normal pressure and is filled with nitrogen for protection, and the solution is heated to 170 ℃ and is exhausted for 30min for heat preservation for later use.
2) The preparation method comprises the steps of (1) preparing InP crystal clusters and short-wave InP quantum dots:
0.3mmol (TMS) was taken 3 P is uniformly dispersed in 1ml of octadecene, the P source is rapidly injected into the 1) by using an injector to react for 5min, and then the temperature is reduced to 30 ℃ at the speed of 2 ℃/min, so that a first mixture is obtained, and the first mixture contains InP clusters and short-wave InP quantum dots with the mass ratio of 4:1.
3) Preparing a long-wave InP quantum dot:
adding 10ml of octadecene into another 50ml of three-neck flask, carrying out low-temperature vacuumizing treatment, converting into exhaust treatment, heating to 280 ℃, then quickly injecting a mixed solution containing InP crystal clusters and short-wave InP quantum dots into high-temperature Octadecene (ODE) for reacting for 20min to obtain a second mixture containing long-wave InP quantum dots, wherein the proportion of residual crystal clusters in the second mixture is 2%, then cooling the temperature to 160 ℃ at a speed of 2 ℃/min, adding 2ml of trioctylphosphine reagent, stirring for 20min, and stopping heating to cool the solution to room temperature.
4) Cleaning InP quantum dots:
adding 3ml of toluene reagent and 15ml of ethanol reagent into the above 3) to form a turbid liquid, and centrifuging the mixed liquid by adopting a centrifugal separation mode to obtain the required InP quantum dots.
Example 2: cdSe QDs are provided
1. Cadmium oleate/Cd (OA) 2 Is prepared from the following steps:
1mmol of CdO and 3ml of Oleic Acid (OA) are added into a 50ml three-neck flask, vacuumizing is carried out for 10min at low temperature, then the mixed solution is heated to 110 ℃ and vacuumized for 2h, after vacuumizing is finished, the mixture is converted into normal pressure, nitrogen is introduced for protection, and the solution is heated to 240 ℃ and exhausted for 30min for heat preservation for later use.
2. Preparation of CdSe crystal clusters and shortwave CdSe quantum dots:
0.3mmol of Se-TOP is uniformly dispersed in 1ml of octadecene, the Se source is rapidly injected into the 1) by using a syringe to react for 5min, and then the temperature is reduced to 50 ℃ at a speed of 3 ℃/min to obtain a first mixture containing CdSe crystal clusters and short wave CdSe quantum dots with a mass ratio of 5:1 for standby.
3. Preparing a long-wave CdSe quantum dot:
adding 10ml of octadecene into another 50ml of three-neck flask, carrying out low-temperature vacuumizing treatment, converting into exhaust treatment, heating to 300 ℃, then quickly injecting a mixed solution containing CdSe crystal clusters and short-wave CdSe quantum dots into high-temperature Octadecene (ODE) for reacting for 20min to obtain a second mixture containing long-wave CdSe quantum dots, wherein the proportion of residual crystal clusters in the second mixture is 3%, then cooling the temperature to 160 ℃ at a speed of 3 ℃/min, adding 2ml of trioctylphosphine reagent, stirring for 20min, and stopping heating to cool the solution to room temperature.
Cleaning CdSe quantum dots:
adding 3ml of toluene reagent and 15ml of ethanol reagent into the solution 3) to form a turbid liquid, and centrifuging the mixed liquid by adopting a centrifugal separation mode to obtain the required CdSe quantum dots.
Example 3: provides a PbS QD
1. Lead oleate/Pb (OA) 2 Is prepared from the following steps:
1mmol of PbO and 3ml of Oleic Acid (OA) are added into a 50ml three-neck flask, vacuumizing is carried out for 10min at low temperature, then the mixed solution is heated to 110 ℃ and vacuumized for 2h, after vacuumizing is finished, the mixture is converted into normal pressure, nitrogen is introduced for protection, and the solution is heated to 90 ℃ and is exhausted for 30min for heat preservation for later use.
2. The preparation method comprises the steps of (1) preparing PbS clusters and short wave PbS quantum dots:
taking 0.3mmol TMS to be uniformly dispersed in 1ml octadecene, rapidly injecting the Pb source into the 1) by using an injector to react for 1min, and then cooling to 30 ℃ at a speed of 4 ℃/min to obtain a first mixture containing PbS clusters and short wave PbS quantum dots with a mass ratio of 3:1 for later use.
3. Preparing a long-wave PbS quantum dot:
adding 10ml of octadecene into another 50ml of three-neck flask, carrying out low-temperature vacuumizing treatment, converting into exhaust treatment, heating to 300 ℃, then quickly injecting mixed solution containing PbS crystal clusters and short-wave PbS quantum dots into high-temperature Octadecene (ODE) for reacting for 20min to obtain a second mixture containing long-wave PbS quantum dots, wherein the proportion of residual crystal clusters in the second mixture is 2%, then cooling the temperature to 120 ℃ at a speed of 3 ℃/min, adding 2ml of trioctylphosphine reagent, stirring for 20min, and stopping heating to cool the solution to room temperature.
Cleaning PbS quantum dots:
adding 3ml of toluene reagent and 15ml of ethanol reagent into the above 3) to form a turbid liquid, and centrifuging the mixed liquid by adopting a centrifugal separation mode to obtain the required PbS quantum dot.
Comparative example 1
The method for synthesizing InP QD by adopting the oil phase method comprises the following specific operation steps:
provides an InP QD
1) indium/In oleate 2 (OA) 3 Is prepared from the following steps:
1mmol of InCl is taken 3 And 3ml of Oleic Acid (OA) are added into a 50ml three-neck flask, vacuumizing is carried out for 10min at low temperature, then vacuumizing is carried out for 2h when the mixed solution is heated to 110 ℃, then the mixture is converted into normal pressure nitrogen for protection after vacuumizing is finished, and the solution is heated to 170 ℃ and is exhausted for 30min for heat preservation for later use.
2) Preparation of InP quantum dots:
1mmol (TMS) 3 P is uniformly dispersed in 1ml of octadecene, and the indium P source is injected into the above 1) by an injector to react for 60min and cooled to 30 ℃ to obtain the InP quantum dot.
3) Cleaning InP quantum dots:
adding 3ml of toluene reagent and 15ml of ethanol reagent into the solution 2) to form a turbid liquid, and centrifuging the mixed liquid by adopting a centrifugal separation mode to obtain the required InP quantum dots.
Comparative example 2
This comparative example is substantially the same as example 1 except that the cooling rate in step 2) in this comparative example is replaced with natural cooling from 2 ℃/min.
Comparative example 3
This comparative example is substantially the same as example 1 except that the cooling rate in step 3) in this comparative example is replaced with natural cooling from 2 ℃/min.
The quantum dots obtained in examples 1 to 3 and comparative examples 1 to 3 were examined as follows:
| example | First exciton peak nm | Valley-peak ratio |
| Example 1 | 580 | 0.83 |
| Example 2 | 567 | 0.85 |
| Example 3 | 550 | 0.79 |
| Comparative example 1 | 580 | 0.51 |
| Comparative example 2 | 580 | 0.67 |
| Comparative example 3 | 580 | 0.70 |
As can be seen from the above table, the first exciton peak of example 1 is clearly visible and has a good valley-peak ratio, indicating that the quantum dot has a relatively excellent uniformity, and that the quantum dots prepared by the conventional method of examples 1 to 3 each have a good valley-peak ratio with respect to comparative example 1, and that the valley-peak ratios of comparative examples 2 and 3 are inferior to those of example 1, but the InP uniformity is still better with respect to comparative example 1.
In summary, the preparation method for improving the size uniformity of the quantum dot provided by the application forms the first mixture containing the binary phase crystal clusters and the short-wave binary phase quantum dots by utilizing the mixed reaction of the cation precursor and the anion precursor, and the binary phase crystal clusters can be effectively formed by effectively controlling the reaction time, the reaction temperature and the reaction termination temperature in the process of forming the first mixture.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of making improved quantum dot size uniformity comprising:
vacuumizing a cation precursor, heating to a first reaction temperature, and reacting an anion precursor with the cation precursor to form a first mixture, wherein the first mixture comprises binary phase clusters and short-wave binary phase quantum dots; cooling to a first termination reaction temperature;
vacuumizing a first organic solvent, heating to a second reaction temperature, and injecting the first mixture into the first organic solvent to react to form a second mixture, wherein the second mixture comprises residual crystal clusters and long-wave binary phase quantum dots; cooling to a second termination reaction temperature;
mixing and stirring the second mixture and a second organic solvent to form a clear and transparent solution, and then cooling to room temperature;
and (3) reacting the clear and transparent solution with a nonpolar reagent and a polar reagent to form a turbid liquid, and then separating to obtain the aqueous solution.
2. The method of claim 1, wherein the binary phase clusters and the short wave binary phase quantum dots have the same composition;
preferably, the binary phase quantum dots include at least one of CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS and CuS;
preferably, the ratio of the binary phase clusters to the binary phase quantum dots is 1-9: 1.
3. the method of claim 1, wherein the first reaction temperature is 80-350 ℃;
preferably, the first termination reaction temperature is 25 ℃ to 300 ℃, and the first termination reaction temperature is lower than the first reaction temperature;
preferably, the first reaction temperature is reduced to the first termination reaction temperature within 25-40min at a speed of 2-4 ℃/min;
preferably, the reaction time of the cationic precursor and the anionic precursor is 10s to 300s;
preferably, the molar ratio of the cationic precursor to the anionic precursor is 1-10:1.
4. The method of claim 1, wherein the residual clusters are less than 5% of the quantum dots in the second mixture after the second mixture is reacted.
5. The method of claim 1, wherein the second reaction temperature is 110 ℃ to 350 ℃;
preferably, the second termination reaction temperature is 80-180 ℃, and the first termination reaction temperature is lower than the first reaction temperature;
preferably, the second reaction temperature is reduced to the second termination reaction temperature within 30-60min at a speed of 2-4 ℃/min.
6. The method of any one of claims 1-5, wherein the cationic precursor comprises Zn (OA) 2 、Cd(OA) 2 、Pb(OA) 2 、In 2 (OA) 3 、Cu(OA) 2 、Ag 2 (OA) 2 、Hg(OA) 2 、Zn(MA) 2 、Cd(MA) 2 、Pb(MA) 2 、In 2 (MA) 3 、Cu(MA) 2 、Ag 2 (MA) 2 、Hg(MA) 2 、Zn(PA) 2 、Cd(PA) 2 、Pb(PA) 2 、In 2 (PA) 3 、Cu(PA) 2 、Ag 2 (PA) 2 、Hg(PA) 2 、Zn(LA) 2 、Cd(LA) 2 、Pb(LA) 2 、In 2 (LA) 3 、Cu(LA) 2 、Ag 2 (LA) 2 And Hg (LA) 2 At least one of them.
7. The method of any one of claims 1-5, wherein the anionic precursor comprises S-ODE, S-TOP, S-OA, se-TOP, S-OLA, S-TBP, se-TBP, te-ODE, te-OA, te-TOP, te-TBP, (TMS) 3 S、(TMS) 3 P and (TMS) 3 At least one of As.
8. The method of any one of claims 1-5, wherein the first organic solvent comprises at least one of octadecene, paraffinic oil, and paraffinic oil;
preferably, the volume ratio of the first organic solvent to the first mixture is 5 to 30:1, a step of;
preferably, the second organic solvent comprises at least one of trioctylphosphine, tributylphosphine, trioctylamine, oleylamine and oleic acid;
preferably, the volume ratio of the second organic solvent to the second mixture is 1: 4-20;
preferably, the reaction time of the second organic solvent and the second mixture is 5-60 min;
preferably, the nonpolar reagent includes at least one of toluene, chloroform, n-hexane, and n-heptane;
preferably, the polar agent comprises at least one of ethanol, methanol, butanol, and isopropanol;
preferably, the volume ratio of the nonpolar reagent to the second mixture is (1-5): 10;
preferably, the volume ratio of the polar agent to the second mixture is (5-15): 10.
9. the method of any one of claims 1-5, wherein evacuating the cationic precursor or the first organic solvent comprises: vacuumizing the cation precursor or the first organic solvent at room temperature, then heating to a vacuumizing temperature, and continuously vacuumizing;
preferably, the vacuumizing temperature is 25-180 ℃;
preferably, after the vacuum-pumping treatment is performed on the cation precursor or the first organic solvent, the method further comprises converting the precursor into normal pressure and introducing a protective gas.
10. A quantum dot prepared by the method of any one of claims 1-9 for improving the uniformity of the size of the quantum dot.
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| US20110223110A1 (en) * | 2008-07-02 | 2011-09-15 | Life Technologies Corporation | Stable indium-containing semiconductor nanocrystals |
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