CN116590014A - Phosphorus-rich quantum dot, preparation method thereof and luminescent material - Google Patents
Phosphorus-rich quantum dot, preparation method thereof and luminescent material Download PDFInfo
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- CN116590014A CN116590014A CN202310562616.7A CN202310562616A CN116590014A CN 116590014 A CN116590014 A CN 116590014A CN 202310562616 A CN202310562616 A CN 202310562616A CN 116590014 A CN116590014 A CN 116590014A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 90
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 56
- 239000011574 phosphorus Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 125000000129 anionic group Chemical group 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical group CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 10
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 10
- 239000012682 cationic precursor Substances 0.000 claims description 9
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 235000021314 Palmitic acid Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 5
- 235000021313 oleic acid Nutrition 0.000 claims description 5
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 3
- AFBKRLAEGBPRAF-UHFFFAOYSA-N N-ethylethanamine phosphane Chemical compound P.C(C)NCC.C(C)NCC.C(C)NCC AFBKRLAEGBPRAF-UHFFFAOYSA-N 0.000 claims description 3
- RACKPBIWIGDYLY-UHFFFAOYSA-N P.C(C)[Si](CC)CC.C(C)[Si](CC)CC.C(C)[Si](CC)CC Chemical compound P.C(C)[Si](CC)CC.C(C)[Si](CC)CC.C(C)[Si](CC)CC RACKPBIWIGDYLY-UHFFFAOYSA-N 0.000 claims description 3
- OBFSIXAGISHRPF-UHFFFAOYSA-N P.CNC.CNC.CNC Chemical compound P.CNC.CNC.CNC OBFSIXAGISHRPF-UHFFFAOYSA-N 0.000 claims description 3
- QYHKPGSSJNYSHJ-UHFFFAOYSA-N P.C[Si](C)C.C[Si](C)C.C[Si](C)C Chemical compound P.C[Si](C)C.C[Si](C)C.C[Si](C)C QYHKPGSSJNYSHJ-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- -1 tris (triphenylsilicon) phosphine Chemical compound 0.000 claims description 3
- 229960002703 undecylenic acid Drugs 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000012688 phosphorus precursor Substances 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 7
- OUMZKMRZMVDEOF-UHFFFAOYSA-N tris(trimethylsilyl)phosphane Chemical compound C[Si](C)(C)P([Si](C)(C)C)[Si](C)(C)C OUMZKMRZMVDEOF-UHFFFAOYSA-N 0.000 description 7
- 238000005253 cladding Methods 0.000 description 6
- 238000005485 electric heating Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000005641 tunneling Effects 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The application discloses the technical field of quantum dot preparation, and discloses a quantum dot, a preparation method thereof and a luminescent material. The preparation method of the phosphorus-rich quantum dot comprises the following steps: controlling the temperature of the mixed solution to be 80-130 ℃, and adding a precursor of anionic phosphorus into the mixed solution to react to generate crystal nucleus; raising the reaction temperature of the system to 220-280 ℃ to enable crystal nucleus to grow into quantum dot nucleus; coating a shell layer outside the quantum dot core; the mixed solution comprises a cation precursor and an acid ligand; the molar ratio of the precursor of anionic phosphorus to the precursor of cationic phosphorus is greater than 1. The disclosed quantum dot is prepared by adopting the preparation method. Disclosed luminescent materials include the quantum dots described above. The preparation method of the phosphorus-rich quantum dot can well solve the problem of too high reaction rate in the existing quantum dot preparation process, and can prepare the quantum dot with short wavelength.
Description
Technical Field
The application relates to the technical field of quantum dot preparation, in particular to a phosphorus-rich quantum dot, a preparation method thereof and a luminescent material.
Background
The quantum dot is an emerging field of solid luminescent materials, has quantum size effect, dielectric confinement effect, macroscopic quantum tunneling effect and the like, and thus has the characteristics of wide and continuous distribution of excitation spectrum, narrow and symmetrical emission spectrum, high optical stability, long fluorescence lifetime and the like, and is widely focused and studied in the display field.
Common quantum dot materials are group II-VI, group III-V, group I-III-VI, etc. At present, II-VI groups of quantum dots are commonly used, and most of the II-VI groups of quantum dots contain heavy metal cadmium (Cd), such as CdS, cdSe and the like, so that the application of the quantum dots is greatly limited due to pollution problems, and along with the importance of the international society on environmental problems, cadmium-free quantum dots are rapidly developed, and the trend of the future quantum dots is that.
The existing quantum dot preparation technology has the defects of over-high reaction rate, difficult mass production, low quantum yield and the like.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a preparation method of phosphorus-rich quantum dots, the quantum dots and a luminescent material.
The application is realized in the following way:
in a first aspect, the present application provides a method for preparing a phosphorus-rich quantum dot, comprising:
controlling the temperature of the mixed solution to be 80-130 ℃, and adding a precursor of anionic phosphorus into the mixed solution to react to generate crystal nucleus;
raising the reaction temperature of the system to 220-280 ℃ to enable crystal nucleus to grow into quantum dot nucleus;
coating a shell layer outside the quantum dot core;
the mixed solution comprises a cation precursor and an acid ligand;
the molar ratio of the precursor of anionic phosphorus to the precursor of cationic phosphorus is greater than 1 and less than or equal to 5.
In an alternative embodiment, the molar ratio of cationic precursor to acid ligand is 1-6:1-2;
in an alternative embodiment, the cationic precursor is selected from at least one of cadmium acetate, zinc chloride, zinc acetate, copper acetate, indium chloride, zinc chloride, and lead chloride.
In an alternative embodiment, the acid ligand is selected from at least one of undecylenic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, and stearic acid.
In an alternative embodiment, the precursor of the anionic phosphorus is selected from at least one of tris (trimethylsilicon) phosphine, tris (triethylsilicon) phosphine, tris (triphenylsilicon) phosphine, tris (dimethylamine) phosphine, and tris (diethylamine) phosphine.
In an alternative embodiment, the inner-to-outer cladding layer is a ZnSe layer and a ZnS layer in sequence.
In an alternative embodiment, adding a precursor of anionic phosphorus into the mixed solution for reaction for 8-12 min to generate crystal nuclei;
optionally, the reaction temperature of the system is increased to 220-280 ℃ and the reaction is carried out for 25-35 min, so that the crystal nucleus grows into a quantum dot nucleus.
In an alternative embodiment, the method further comprises preparing the mixed solution prior to adding the precursor of the anionic phosphorus to the mixed solution, the method comprising:
heating the cationic precursor, acid ligand and solvent in a vessel to dissolve;
alternatively, the solvent is 1-octadecene.
In a second aspect, the present application provides a phosphorus-rich quantum dot, prepared by a method according to any one of the preceding embodiments.
In a third aspect, the present application provides a luminescent material comprising the quantum dots of the previous embodiments.
The application has the following beneficial effects:
1. forming crystal nucleus at low temperature (80-130 ℃) and reacting at the subsequent growth temperature (220-280 ℃) to obtain quantum dot nuclei with more uniform size;
2. the precursor of the anionic phosphorus is added according to the proportion that the molar ratio of the precursor of the anionic phosphorus to the precursor of the cationic phosphorus is more than 1 and less than or equal to 5, so that the surface of the quantum dot core is rich in phosphorus, the surface defect can be well compensated, and better luminous intensity is provided;
3. the problem of too high reaction rate in the existing quantum dot preparation process can be well solved by the phosphorus-rich quantum dot in a low-temperature state, and the quantum dot with a shorter wavelength can be prepared.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application 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 quantum dot, the preparation method thereof and the luminescent material provided by the embodiment of the application are specifically described below.
The preparation method of the phosphorus-rich quantum dot provided by the embodiment of the application comprises the following steps:
controlling the temperature of the mixed solution to be 80-130 ℃, and adding a precursor of anionic phosphorus into the mixed solution to react to generate crystal nucleus;
raising the reaction temperature of the system to 220-280 ℃ to enable crystal nucleus to grow into quantum dot nucleus;
coating a shell layer outside the quantum dot core;
the mixed solution comprises a cation precursor and an acid ligand;
the molar ratio of the precursor of anionic phosphorus to the precursor of cationic phosphorus is greater than 1 and less than or equal to 5.
According to the preparation method provided by the embodiment of the application, the precursor of the anionic phosphorus is added at low temperature, crystal nucleus is formed at low temperature (80-130 ℃), and quantum dot cores with more uniform size can be obtained through reaction at the subsequent growth temperature (220-280 ℃); the precursor of the anionic phosphorus is added according to the proportion that the molar ratio of the precursor of the anionic phosphorus to the precursor of the cationic phosphorus is more than 1 and less than or equal to 5, so that the surface of the quantum dot core is rich in phosphorus, the surface defect can be well compensated, and better luminous intensity is provided; and the problem of too high reaction rate in the existing quantum dot preparation process can be well solved by the phosphorus enrichment under the low-temperature state, and the quantum dot with a shorter wavelength can be prepared.
Specifically, the preparation method comprises the following steps:
s1, dissolving cation precursor
Adding a solvent, a cation precursor and an acid ligand into a three-neck flask with magnetic stirring and electric heating sleeves, heating to 160-200 ℃ (e.g. 160 ℃, 180 ℃ or 200 ℃) in a vacuum exhaust state, stirring to completely dissolve solid powder, and uniformly mixing to obtain a mixed solution;
the acid ligand plays a role in dissolving the cation precursor, and the molar ratio of the cation precursor to the acid ligand is 1:2-1:6 (for example, 1:1, 1:2, 1:3, 1:4, 1:5 or 1:6) to realize a faster dissolving effect.
The solvent provides a solution environment for the reaction system, and optionally, the solvent is 1-octadecene. For example, when the reaction is carried out in a 100ml reaction vessel, the amount thereof may be generally 5 to 10ml.
Optionally, the cationic precursor is selected from at least one of cadmium acetate, zinc chloride, zinc acetate, copper acetate, indium chloride, zinc chloride, and lead chloride.
Optionally, the acid ligand is selected from at least one of undecylenic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, and stearic acid.
S2, generating crystal nucleus (cluster) by reaction
Vacuumizing the reaction vessel, then changing argon gas into exhaust, controlling the temperature of the mixed solution to be 80-130 ℃, and adding the precursor of the anionic phosphorus into the mixed solution to react for 8-12 min to generate crystal nuclei (cluster). The molar ratio of the addition of the precursor of anionic phosphorus to the cationic precursor is greater than 1 and less than or equal to 5 (the ratio is for example 1.1, 2, 3, 4 or 5).
The phosphorus-rich state at low temperature can well solve the problem of too high reaction rate in the existing quantum dot preparation process, and the quantum dot with shorter wavelength can be prepared.
Alternatively, the precursor of anionic phosphorus is selected from at least one of tris (trimethylsilicon) phosphine, tris (triethylsilicon) phosphine, tris (triphenylsilicon) phosphine, tris (dimethylamine) phosphine, and tris (diethylamine) phosphine.
S3, preparing the quantum dot core
The temperature of the reaction system is raised to 220-280 ℃ (220 ℃, 230 ℃, 250 ℃, 270 ℃ or 280 ℃), and the reaction is carried out for 25-35 min (25 min, 30min or 35min, for example) so that crystal nuclei grow into quantum dot nuclei.
S4, coating shell layer
And coating a shell layer outside the quantum dot core by the existing shell layer coating method.
Alternatively, the coated shell layer may be a ZnSe layer and a ZnS layer in this order, for example, from inside to outside.
Alternatively, the method of coating the shell layer may be, for example: and dropwise adding the Se precursor and the S precursor at high temperature.
The phosphorus-rich quantum dot provided by the embodiment of the application is prepared by adopting the preparation method provided by the embodiment of the application. The quantum dot has a core with uniform size, shorter wavelength and better luminous intensity.
The luminescent material provided by the embodiment of the application comprises the quantum dots provided by the embodiment of the application. The luminescent material has better luminescent property due to the quantum dots provided by the embodiment of the application.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of a phosphorus-rich quantum dot, which comprises the following steps:
(1) 8ml of 1-octadecene, 2.0mmol of In (Ac) 3 (indium acetate) and 1.0mmol of OA (oleic acid) are added into a three-neck flask provided with a magnetic stirring sleeve and an electric heating sleeve, the mixture is heated to 180 ℃ In a vacuum exhaust state, solid powder is completely dissolved by stirring, and a mixed solution is obtained by uniformly mixing;
(2) Vacuumizing the three-mouth bottle for 60min and changing the three-mouth bottle into Ar 2 Exhausting, reducing the temperature of the mixed solution to 90 ℃ and injecting 3.2mmol (TMS) 3 P (tris (trimethylsilyl) phosphine) for 10min to form nuclei (clusters);
(3) And (3) raising the temperature of the reaction system to 230 ℃ for reaction for 30min, so that crystal nuclei grow into quantum dot nuclei.
(4) And cleaning the quantum dot core, and then sequentially carrying out ZnSe layer and ZnS layer cladding shell layer to obtain the quantum dot with the core-shell structure. The specific coating method comprises the following steps: se-TOP 2.0mmol and S-TOP1.0mmol were added dropwise at 305 ℃.
Example 2
The embodiment provides a preparation method of a phosphorus-rich quantum dot, which comprises the following steps:
(1) In a three-neck flask with magnetic stirring and an electric heating sleeve, adding 10ml of 1-octadecene, 1.6mmol of In (Ac) 3 (indium acetate) and 5.0mmol of PA (palmitic acid), heating to 180 ℃ In a vacuum exhaust state, stirring to completely dissolve solid powder, and uniformly mixing to obtain a mixed solution;
(2) Vacuumizing the three-mouth bottle for 60min and changing the three-mouth bottle into Ar 2 Exhausting, reducing the temperature of the mixed solution to 80 ℃ and injecting 4.5mmol (TMS) 3 P (tris (trimethylsilyl) phosphine) for 10min to form nuclei (clusters);
(3) And (3) raising the temperature of the reaction system to 260 ℃ for reaction for 30min, so that crystal nuclei grow into quantum dot nuclei.
(4) And cleaning the quantum dot core, and then sequentially carrying out ZnSe layer and ZnS layer cladding shell layer to obtain the quantum dot with the core-shell structure. The specific coating method comprises the following steps: se-TOP 2.2mmol and S-TBP 1.0mmol were added dropwise at 305 ℃.
Example 3
The embodiment provides a preparation method of a phosphorus-rich quantum dot, which comprises the following steps:
(1) In a three-neck flask with magnetic stirring and electric heating sleeve, adding 6ml of 1-octadecene, 1.2mmol of In (Ac) 3 (indium acetate) and 3.8mmol of LA (dodecanoic acid), heating to 180 ℃ In a vacuum exhaust state, stirring to completely dissolve solid powder, and uniformly mixing to obtain a mixed solution;
(2) Vacuumizing the three-mouth bottle for 60min and changing the three-mouth bottle into Ar 2 Exhausting, reducing the temperature of the mixed solution to 100 ℃, and pumping 5.0mmol of tris (diethyl amine) phosphine for reaction for 10min to form crystal nuclei (clusters);
(3) And (3) raising the temperature of the reaction system to 280 ℃ for reaction for 30min, so that crystal nuclei grow into quantum dot nuclei.
(4) And cleaning the quantum dot core, and then sequentially carrying out ZnSe layer and ZnS layer cladding shell layer to obtain the quantum dot with the core-shell structure. The specific coating method comprises the following steps: se-TOP 2.0mmol and S-TBP 1.0mmol were added dropwise at 305 ℃.
Example 4
The embodiment provides a preparation method of a phosphorus-rich quantum dot, which comprises the following steps:
(1) In a three-necked flask equipped with magnetic stirring and electric heating mantle, 10ml of 1-octadecene and 1.5mmol of InCl were added 3 (indium chloride) and 3.8mmolOA (oleic acid) is heated to 180 ℃ in a vacuum exhaust state, stirred to completely dissolve solid powder, and uniformly mixed to obtain a mixed solution;
(2) Vacuumizing the three-mouth bottle for 60min and changing the three-mouth bottle into Ar 2 Exhausting, reducing the temperature of the mixed solution to 90 ℃ and injecting 1.56mmol (TMS) 3 P (tris (trimethylsilyl) phosphine) for 10min to form nuclei (clusters);
(3) And (3) raising the temperature of the reaction system to 240 ℃ for reaction for 30min, so that crystal nuclei grow into quantum dot nuclei.
(4) And cleaning the quantum dot core, and then sequentially carrying out ZnSe layer and ZnS layer cladding shell layer to obtain the quantum dot with the core-shell structure. The specific coating method comprises the following steps: se-TOP 2.0mmol and S-TBP 1.0mmol were added dropwise at 305 ℃.
Example 5
The embodiment provides a preparation method of a phosphorus-rich quantum dot, which comprises the following steps:
(1) Into a three-necked flask equipped with magnetic stirring and electric heating jacket, 8ml of 1-octadecene and 1.8mmol of InCl were charged 3 (indium chloride) and 1.5mmol of LA (dodecanoic acid) are heated to 180 ℃ in a vacuum exhaust state, and stirred to completely dissolve solid powder, and uniformly mixed to obtain a mixed solution;
(2) Vacuumizing the three-mouth bottle for 60min and changing the three-mouth bottle into Ar 2 Exhausting, reducing the temperature of the mixed solution to 80 ℃ and injecting 3.6mmol (TMS) 3 P (tris (trimethylsilyl) phosphine) for 10min to form nuclei (clusters);
(3) And (3) raising the temperature of the reaction system to 230 ℃ for reaction for 30min, so that crystal nuclei grow into quantum dot nuclei.
(4) And cleaning the quantum dot core, and then sequentially carrying out ZnSe layer and ZnS layer cladding shell layer to obtain the quantum dot with the core-shell structure. The specific coating method comprises the following steps: se-TOP 2.5mmol and S-TBP 1.0mmol were added dropwise at 305 ℃.
Example 6
This embodiment is substantially the same as embodiment 1, except that: the temperature of the mixed solution is reduced to 130 ℃ and then the mixed solution is injected (TMS) 3 P (tris (trimethylsilyl) phosphine).
Comparative example 1
This comparative example is substantially the same as example 6, except that: in the step (2), the temperature of the mixed solution is controlled to 150 ℃, and TMS is injected into the mixed solution 3 P (tris (trimethylsilyl) phosphine).
Comparative example 2
This comparative example is substantially the same as example 1, except that: driven in (TMS) 3 The amount of P (tris (trimethylsilyl) phosphine) was 1.8mmol.
Experimental example
The quantum dots prepared in examples 1 to 6 and comparative examples 1 and 2 were tested for absorption (UV) and emission (PL), and quantum efficiencies were calculated.
The test method is to dilute the quantum dot into normal hexane solution, test the absorption value and the emission peak area by an ultraviolet spectrophotometer and a fluorescence spectrophotometer respectively, compare the absorption value with dye (quantum efficiency is 100%) by dividing the emission peak area, and calculate the quantum efficiency. The test results are recorded in table 1.
TABLE 1 Performance test results records for the example and comparative example quantum dots
| Group of | Absorption (UV) | Emission (PL) peak area | Quantum efficiency |
| Example 1 | 0.0258 | 30753 | 93.6％ |
| Example 2 | 0.0265 | 32127 | 95.2％ |
| Example 3 | 0.0325 | 37043 | 89.5％ |
| Example 4 | 0.0358 | 41761 | 91.6％ |
| Example 5 | 0.0249 | 30854 | 97.3％ |
| Example 6 | 0.0321 | 37405 | 91.5％ |
| Comparative example 1 | 0.0268 | 28873 | 84.6％ |
| Comparative example 2 | 0.0294 | 29391 | 78.5％ |
The baseline of the dye is 1273500, and the quantum dots prepared by the embodiment of the application have better luminous performance as can be seen from the table. Comparing example 6 with comparative example 1, the quantum efficiency of the quantum dot prepared in comparative example 1 is significantly worse, indicating that if the temperature is too high when the precursor of anionic phosphorus is added, nucleation of the quantum dot is detrimental; comparing example 1 with comparative example 2, the quantum efficiency of the quantum dot prepared in comparative example 2 is significantly worse, indicating that if the amount of the precursor of the added anionic phosphorus is small, and phosphorus enrichment cannot be achieved, nucleation is disadvantageous, and higher quantum efficiency cannot be obtained for the subsequent growth shell layer.
In summary, the preparation method provided by the embodiment of the application has the following advantages:
1. forming crystal nucleus at low temperature (80-130 ℃) and reacting at the subsequent growth temperature (220-280 ℃) to obtain quantum dot nuclei with more uniform size;
2. the precursor of the anionic phosphorus is added according to the proportion that the molar ratio of the precursor of the anionic phosphorus to the precursor of the cationic phosphorus is more than 1 and less than or equal to 5, so that the surface of the quantum dot core is rich in phosphorus, the surface defect can be well compensated, and better luminous intensity is provided;
3. the problem of too high reaction rate in the existing quantum dot preparation process can be well solved by the phosphorus-rich quantum dot in a low-temperature state, and the quantum dot with a shorter wavelength can be prepared.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the phosphorus-rich quantum dot is characterized by comprising the following steps of:
controlling the temperature of the mixed solution to be 80-130 ℃, and adding a precursor of anionic phosphorus into the mixed solution to react to generate crystal nucleus;
raising the reaction temperature of the system to 220-280 ℃ to enable crystal nucleus to grow into quantum dot nucleus;
coating a shell layer outside the quantum dot core;
the mixed solution comprises a cation precursor and an acid ligand;
the molar ratio of the anionic phosphorus precursor to the cationic precursor is greater than 1 and less than or equal to 5.
2. The method of claim 1, wherein the molar ratio of the cationic precursor to the acid ligand is 1:2 to 1:6.
3. The method of claim 1, wherein the cationic precursor is selected from at least one of cadmium acetate, zinc chloride, zinc acetate, copper acetate, indium chloride, zinc chloride, and lead chloride.
4. The method of claim 1, wherein the acid ligand is at least one selected from undecylenic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, and stearic acid.
5. The method of preparing according to claim 1, wherein the precursor of anionic phosphorus is selected from at least one of tris (trimethylsilicon) phosphine, tris (triethylsilicon) phosphine, tris (triphenylsilicon) phosphine, tris (dimethylamine) phosphine, and tris (diethylamine) phosphine.
6. The preparation method according to claim 1, wherein the shell layer coated from inside to outside is a ZnSe layer and a ZnS layer in sequence.
7. The method according to claim 1, wherein the precursor of the anionic phosphorus is added to the mixed solution and reacted for 8 to 12 minutes to generate the crystal nuclei;
optionally, the reaction temperature of the system is increased to 220-280 ℃ and the reaction is carried out for 25-35 min, so that the crystal nucleus grows into the quantum dot nucleus.
8. The method of preparing according to claim 1, further comprising preparing the mixed solution before adding the precursor of anionic phosphorus to the mixed solution, the method of preparing comprising:
heating the cationic precursor, acid ligand and solvent in a vessel to dissolve;
alternatively, the solvent is 1-octadecene.
9. A phosphorus-rich quantum dot prepared by the preparation method according to any one of claims 1 to 8.
10. A luminescent material comprising the quantum dot according to claim 9.
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