CN115477947B - Mercury-based chalcogen compound quantum dot, preparation method thereof and sensor - Google Patents
Mercury-based chalcogen compound quantum dot, preparation method thereof and sensor Download PDFInfo
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- CN115477947B CN115477947B CN202210996542.3A CN202210996542A CN115477947B CN 115477947 B CN115477947 B CN 115477947B CN 202210996542 A CN202210996542 A CN 202210996542A CN 115477947 B CN115477947 B CN 115477947B
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 88
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 48
- 150000001786 chalcogen compounds Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000004770 chalcogenides Chemical class 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 29
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 150000002730 mercury Chemical class 0.000 claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 5
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 claims description 4
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical group Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 4
- JPJGNZQDELRZGE-UHFFFAOYSA-N (phenyl-$l^{2}-phosphanyl)benzene Chemical compound C=1C=CC=CC=1[P]C1=CC=CC=C1 JPJGNZQDELRZGE-UHFFFAOYSA-N 0.000 claims description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002523 mercuric chloride Drugs 0.000 claims description 3
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 claims description 3
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001987 mercury nitrate Inorganic materials 0.000 claims description 2
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 claims description 2
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000012984 biological imaging Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YFDLHELOZYVNJE-UHFFFAOYSA-L mercury diiodide Chemical compound I[Hg]I YFDLHELOZYVNJE-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229960003671 mercuric iodide Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/89—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing mercury
- C09K11/892—Chalcogenides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D5/00—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
- G01D5/26—Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
Abstract
The invention discloses a mercury-based chalcogen compound quantum dot, a preparation method thereof and a sensor. The method comprises the following steps: adding mercury salt into a first solvent to obtain a first mixture; adding an organic phosphorus and cadmium-based chalcogen compound quantum dot solution into the first mixture to obtain a second mixture; and adding a second solvent into the second mixture to obtain the mercury-based chalcogenide quantum dots. The invention prepares the monodisperse, excellent optical property and high-quality mercury-based chalcogenides quantum dots through simple solid-liquid interface reaction, and compared with the traditional synthesis process, the invention has simple and controllable process and higher yield, can be prepared in large scale, and has wide application prospect in the fields of biological imaging, infrared photoelectric devices and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of compound semiconductor nano materials, and particularly relates to mercury-based chalcogen compound quantum dots, a preparation method thereof and a sensor.
Background
The infrared photoelectric detector plays an important role in the fields of weather forecast, safety monitoring, medical images, optical communication and the like. However, high performance infrared photodetectors are typically based on expensive high vacuum deposition of HgCdTe or InGaAs produced, which limits their large scale commercial application. Compared with an epitaxial material, the colloidal quantum dots can change the size of the nano particles, and the wide adjustability of the infrared broad spectrum is provided. Because the quantum dots are synthesized in the liquid phase, the used reagent is relatively cheap, the cost is low, and the yield is high.
In the short-wave infrared response range, reported lead-based chalcogenide and mercury-based chalcogenide quantum dot photodetectors include phototransistors, photoconductive devices, and photodiodes. The spherical mercury-based chalcogenides quantum dots have the advantages that: is easy to adjust within the range of 1-3 mu m, has stronger light absorption coefficient, lower Auger coefficient and higher photoluminescence efficiency. However, in previously developed synthetic routes, mercury-based chalcogenide quantum dots synthesized based on trioctyl phosphorus have poor surface stability, resulting in uncontrolled quantum dot morphology and coagulation. Although highly monodisperse, spherical mercury-based chalcogenide quantum dots of excellent optical properties have been reported, the need for the expensive tellurium precursor, bis (trimethylsilyl) tellurium, further hampers commercial application of mercury-based chalcogenide quantum dots.
Disclosure of Invention
In order to solve the technical problems, the invention provides the mercury-based chalcogenides quantum dot, the preparation method thereof and the sensor, which can accurately design the components and the optical properties of the quantum dot, have high repeatability, simple operation and high yield, and are suitable for large-scale industrialized production.
In a first aspect, the present invention provides a method of preparing mercury-based chalcogenide quantum dots, the method comprising: adding mercury salt into a first solvent to obtain a first mixture; adding an organic phosphorus and cadmium-based chalcogen compound quantum dot solution into the first mixture to obtain a second mixture; and adding a second solvent into the second mixture to obtain the mercury-based chalcogenide quantum dots.
Wherein the method further comprises: the cadmium-based chalcogenide quantum dot solid is dissolved in a first solvent to form a cadmium-based chalcogenide quantum dot solution.
Wherein, the step of adding mercury salt into the first solvent to obtain a first mixture comprises the following steps: adding mercury salt into a first solvent, carrying out oscillation reaction, and then standing; the step of adding the organic phosphorus and cadmium-based chalcogen compound quantum dot solution into the first mixture to obtain a second mixture comprises the following steps: adding the cadmium-based chalcogen compound quantum dot solution into the first mixture, and stirring at normal temperature to obtain a third mixture; adding organic phosphorus into the third mixture, and heating for reaction to obtain a fourth mixture; and carrying out quenching reaction on the fourth mixture by using the first solvent to obtain the second mixture.
Wherein the first solvent comprises any one or any combination of n-hexane, n-octane, toluene, tetrachloroethylene and chloroform.
Wherein the second solvent comprises any one or any combination of ethanol, methanol, isopropanol, acetone and acetonitrile.
Wherein the concentration of the cadmium-based chalcogen compound quantum dot solution is 1 mg/mL-1000 mg/mL.
Wherein the mercury salt is mercuric chloride HgCl 2 Mercuric bromide HgBr 2 Mercury iodide HgI 2 Hg (Ac) mercuric acetate 2 And mercury nitrate HgNO 3 Any one or any combination of the above.
Wherein the organic phosphorus is any one or any combination of trioctyl phosphorus, tributyl phosphorus, diphenyl phosphorus, trioctyl phosphorus oxide and triphenyl phosphorus.
In a second aspect, the present invention provides a mercury-based chalcogenide quantum dot prepared using the method of any one of the above; wherein the diameter of the mercury-based chalcogenide quantum dot is 2-25 nm, the size distribution is uniform, and the wavelength of the absorption band edge is infrared 1-3 mu m.
In a third aspect, the present invention provides a sensor comprising any one of a biological imaging sensor, an infrared photoelectric sensor; the sensor comprises a functional layer comprising mercury-based chalcogenide quantum dots prepared by the method of any one of the above.
The method has the beneficial effects that mercury salt is added into the first solvent to obtain a first mixture; adding an organic phosphorus and cadmium-based chalcogen compound quantum dot solution into the first mixture to obtain a second mixture; and adding a second solvent into the second mixture to obtain the mercury-based chalcogenide quantum dots. Under the catalysis of organic phosphorus, the cation exchange exchanges cadmium-based chalcogen compound quantum dots to mercury-based chalcogen compound quantum dots, so that the components and optical properties of the quantum dots can be accurately designed, the photoelectric performance of the quantum dots is optimized, and the cost is reduced. The method has the advantages of high repeatability, simple operation and high yield, and is suitable for large-scale industrialized production.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be given of the drawings used in the embodiments or the description of the prior art, it being obvious that the drawings described below are only examples of the invention herein, and that other drawings can be obtained from these drawings without the inventive effort of a person skilled in the art.
FIG. 1 is a schematic flow chart of one embodiment of a method for preparing mercury-based chalcogenide quantum dots according to the present invention;
FIG. 2 is an absorption spectrum of a mercury-based chalcogenide quantum dot according to the invention;
FIG. 3 is a powder X-ray diffraction pattern of a mercury-based chalcogenide quantum dot in accordance with the present invention;
fig. 4 is a transmission photomicrograph of a mercury based chalcogenide quantum dot according to the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples.
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing a mercury-based chalcogenide quantum dot according to the present invention, which specifically includes:
step S11: mercury salt is added into the first solvent to obtain a first mixture.
Specifically, mercury salt is added into a first solvent, and the mixture is subjected to oscillation reaction and then is left to stand. Wherein the oscillation time is 1-10 minutes, and the standing time is 6 minutes.
Step S12: adding an organic phosphorus and cadmium-based chalcogen compound quantum dot solution into the first mixture to obtain a second mixture.
Specifically, the cadmium-based chalcogen compound quantum dot solution is added into the first mixture, and stirring is carried out at normal temperature, so that a third mixture is obtained. The stirring at normal temperature can be performed by magnetic stirring on a heating table for 1 minute to 10 days. Adding organic phosphorus into the third mixture, and heating for reaction to obtain a fourth mixture; and carrying out quenching reaction on the fourth mixture by using the first solvent to obtain the second mixture. In one embodiment, the adding of the cadmium-based chalcogenide quantum dot solution to the first mixture is actually a rapid injection of the cadmium-based chalcogenide quantum dot solution into the first mixture located within a glass vial using a syringe.
After adding organic phosphorus into the third mixture, heating to a preset temperature and reacting for a preset time to obtain a fourth mixture. The preset temperature range is normal temperature to 300 ℃, and the preset time is within 1 minute to 10 days. In the quenching reaction, the first solvent is at a low temperature, that is, the fourth mixture is quenched with the cold first solvent to obtain the second mixture.
In one embodiment, a cadmium-based chalcogenide quantum dot solution is prepared first, and specifically, a cadmium-based chalcogenide quantum dot solid is dissolved in a first solvent to form a cadmium-based chalcogenide quantum dot solution. Alternatively, the size of the cadmium-based chalcogenide quantum dots is 1-100nm. Optionally, the ligand on the surface of the cadmium-based chalcogen compound quantum dot is oleic acid, oleylamine, octadecylamine, dodecyl mercaptan or octyl mercaptan.
Step S13: and adding a second solvent into the second mixture to obtain the mercury-based chalcogenide quantum dots.
Specifically, adding a second solvent into the second mixture, centrifuging to precipitate the quantum dots from the system, removing the upper liquid, and adding a nonpolar solvent to disperse the quantum dots to obtain the mercury-based chalcogenide quantum dots. The centrifugation speed was 3000r/min to 13000r/min.
In one embodiment, the above step S13 may be repeated 3 times or more for the effect of the mercury-based chalcogenide quantum dots.
In an embodiment, the first solvent includes any one or any combination of n-hexane, n-octane, toluene, tetrachloroethylene, chloroform.
In an embodiment, the second solvent includes any one or any combination of ethanol, methanol, isopropanol, acetone, acetonitrile.
In one embodiment, the concentration of the cadmium-based chalcogenide quantum dot solution is 1 mg/mL-1000 mg/mL.
In an embodiment, the mercury salt is any one or any combination of mercuric chloride HgCl2, mercuric bromide HgBr2, mercuric iodide HgI2, mercuric acetate Hg (Ac) 2, and mercuric nitrate HgNO 3.
In one embodiment, the organic phosphorus is any one or any combination of trioctyl phosphorus, tributyl phosphorus, diphenyl phosphorus, trioctyl phosphorus oxide and triphenyl phosphorus.
Compared with the traditional technology, the mercury-based chalcogen compound quantum dot prepared in the traditional technology has the defects of uncontrollable quantum dot morphology, easy coagulation, high precursor requirement and the like. The mercury-based chalcogenide quantum dots with expected size and morphology can be prepared from the cadmium-based chalcogenide quantum dot template by only one-step reaction. The method provided by the invention is more controllable, quicker and cheaper than the traditional method, so the method has the potential of industrialized production compared with the former method.
The preparation process of the invention can be expanded to other alloy quantum dot systems, such as CdSe to Hg x Cd 1-x Se, cdS to Hg x Cd 1-x S, cdTe, pbTe and the like, has high yield, convenient operation, mild reaction and easy mass production.
The method for preparing the mercury-based chalcogenide quantum dots of the present application is described below by way of specific examples.
Example 1
Weighing HgCl with an electronic balance 2 272mg of powder is dispersed in 10mL of toluene, the mixture is vibrated for 10min, the mixture is kept stand for 6min, 100 mu L of trioctyl phosphorus is added, 1mg/mL of cadmium-based chalcogen compound quantum dot solution is injected, the temperature is quickly raised to 60 ℃, the reaction is carried out for 30min, 30mL of ethanol is added, 6000rmp is centrifuged for 2min, and upper liquid is poured off after centrifugation, so that the lower mercury-based chalcogen compound quantum dot solid powder is obtained.
Example 2
Weighing HgCl with an electronic balance 2 272mg of powder is dispersed in 10mL of n-octane, oscillated for 10min, stood for 6min, 1mL of trioctyl phosphorus is added, 1000mg/mL of cadmium-based chalcogen compound quantum dot solution is injected, the temperature is quickly raised to 200 ℃, the reaction is carried out for 10 days, 20mL of acetone is added, 6000rmp is centrifuged for 2min, the upper liquid is poured off after centrifugation, and the lower mercury-based chalcogen compound quantum dot solid powder is obtained. Referring to fig. 2, a real-time absorption spectrum of the mercury-based chalcogenide quantum dot according to the present embodiment is shown, which illustrates the precise control of the mercury-based chalcogenide quantum dot according to the present invention.
Example 3
Weighing HgI with electronic balance 2 And HgBr 2 272mg of powder is dispersed in 10mL of normal hexane, the mixture is vibrated for 10min, the mixture is kept stand for 6min, 100 mu L of trioctyl phosphorus is added, 500mg/mL of cadmium-based chalcogen compound quantum dot solution is injected, the temperature is quickly raised to 60 ℃, the reaction is carried out for 30min, 10mL of isopropanol is added, 6000rmp is centrifuged for 2min, and upper liquid is poured off after centrifugation, so that the lower mercury-based chalcogen compound quantum dot solid powder is obtained. Referring to fig. 3, an X-ray powder diffraction pattern of the mercury-based chalcogenide quantum dots according to this example can be seen to be a standard cubic phase structure of the mercury-based chalcogenide quantum dots.
Example 4
Weighing HgI with electronic balance 2 And HgCl 2 272mg of each powder is dispersed in 10mL of normal hexane, the mixture is vibrated for 10min, the mixture is kept stand for 6min, 100 mu L of trioctyl phosphorus is added, 500mg/mL of cadmium-based chalcogen compound quantum dot solution is injected, the temperature is quickly raised to 60 ℃, the reaction is carried out for 30min, 20mL of acetonitrile is added, 6000rmp is centrifuged for 2min, and upper liquid is poured off after centrifugation, so that the lower mercury-based chalcogen compound quantum dot solid powder is obtained. Referring to fig. 4, a transmission microscope image of the mercury-based chalcogenide quantum dots with high monodispersion and uniform size is prepared from the mercury-based chalcogenide quantum dot raw material in this example. As can be seen from FIG. 4, the mercury-based chalcogenide quantum dots obtained in this example have the same morphology as the parent CdTe quantum dots, and have uniform size dispersion of about 5.4nm and absorption wavelength of 1.4 μm.
In addition, the inventor also uses other raw materials listed above and other process conditions to replace various raw materials and corresponding process conditions in examples 1-4, and the obtained infrared mercury-based chalcogenide quantum dots have ideal morphology, performance and the like, and are basically similar to the products in examples 1-4.
In conclusion, the invention utilizes a mild solid-liquid interface to efficiently realize the conversion from the cadmium-based chalcogen compound quantum dot to the mercury-based chalcogen compound quantum dot, has simple and controllable synthesis process, higher yield, low cost and large-scale preparation, and the obtained product has uniform size, continuously adjustable absorption band of 1-3 mu m in infrared, excellent light stability and wide application prospect in the fields of biological imaging, infrared devices and the like.
The invention also provides a mercury-based chalcogenide quantum dot which is prepared by the method shown in the figure 1. Wherein the diameter of the mercury-based chalcogenide quantum dot is 2-25 nm, the size distribution is uniform, and the wavelength of the absorption band edge is infrared 1-3 mu m.
The invention also provides a sensor, which comprises any one of a biological imaging sensor and an infrared photoelectric sensor; the sensor comprises a functional layer comprising mercury-based chalcogenide quantum dots prepared using the method described above with respect to fig. 1.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
The use of the terms "comprising," "having," and "including" are generally understood to be open-ended and not limiting, unless specifically stated otherwise.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously. While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
The foregoing is only an implementation method of the present invention, and is not limited to the patent scope of the present invention, and all equivalent structures or equivalent processes using the descriptions of the present invention and the accompanying drawings, or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (6)
1. A method of preparing mercury-based chalcogenide quantum dots, the method comprising:
adding mercury salt into a first solvent to obtain a first mixture;
adding an organic phosphorus and cadmium-based chalcogen compound quantum dot solution into the first mixture to obtain a second mixture;
adding a second solvent into the second mixture to obtain mercury-based chalcogenide quantum dots;
the first solvent comprises any one or any combination of n-hexane, n-octane, toluene, tetrachloroethylene and chloroform.
2. The method according to claim 1, wherein the method further comprises:
the cadmium-based chalcogenide quantum dot solid is dissolved in a first solvent to form a cadmium-based chalcogenide quantum dot solution.
3. The method of claim 1, wherein: the second solvent comprises any one or any combination of ethanol, methanol, isopropanol, acetone and acetonitrile.
4. The method of claim 2, wherein the cadmium-based chalcogenide quantum dot solution has a concentration of 1mg/mL to 1000mg/mL.
5. The method of claim 1, wherein the mercury salt is mercuric chloride HgCl 2 Mercuric bromide HgBr 2 Mercury iodide HgI 2 Hg (Ac) mercuric acetate 2 And mercury nitrate HgNO 3 Any one or any combination of the above.
6. The method of claim 1, wherein the organophosphorus is any one or any combination of trioctyl phosphorus, tributyl phosphorus, diphenyl phosphorus, trioctyl phosphorus oxide, and triphenyl phosphorus.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311383A (en) * | 2008-03-11 | 2008-11-26 | 河南大学 | Semiconductor nanocrystalline and method for preparing same |
| CN103131420A (en) * | 2012-12-25 | 2013-06-05 | 深圳先进技术研究院 | Preparation method and application of CdHgTe quantum dot solution, CdHgTe quantum dot and bimodal semiconductor nanometer material |
| CN103484123A (en) * | 2013-09-22 | 2014-01-01 | 天津晟宝量子点制造有限公司 | Novel preparation method for ternary alloy type CdSeS quantum dots |
| CN111977617A (en) * | 2019-05-22 | 2020-11-24 | 北京理工大学 | Method for preparing cadmium-based alloy nano material |
-
2022
- 2022-08-19 CN CN202210996542.3A patent/CN115477947B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311383A (en) * | 2008-03-11 | 2008-11-26 | 河南大学 | Semiconductor nanocrystalline and method for preparing same |
| CN103131420A (en) * | 2012-12-25 | 2013-06-05 | 深圳先进技术研究院 | Preparation method and application of CdHgTe quantum dot solution, CdHgTe quantum dot and bimodal semiconductor nanometer material |
| CN103484123A (en) * | 2013-09-22 | 2014-01-01 | 天津晟宝量子点制造有限公司 | Novel preparation method for ternary alloy type CdSeS quantum dots |
| CN111977617A (en) * | 2019-05-22 | 2020-11-24 | 北京理工大学 | Method for preparing cadmium-based alloy nano material |
Non-Patent Citations (3)
| Title |
|---|
| Electronic Impurity Doping in CdSe Nanocrystals;Ayaskanta Sahu,etc;《Nano Lett. 》;第12卷;2587-2594 * |
| The room-temperature structural and optical transformation of cadmium chalcogenide quantum dots triggered by reactive cations;Shohei Taniguchi，etc;《 J. Mater. Chem.》;第21卷;11592-11598 * |
| The Room-Temperature Synthesis of Anisotropic CdHgTe Quantum Dot Alloys: A "Molecular Welding" Effect;Shohei Taniguchi，etc;《J. Am. Chem. Soc.》;第133卷;3328-3331 * |
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