CN105419778B - A kind of quantum dot composite material containing paraffin and preparation method thereof - Google Patents
A kind of quantum dot composite material containing paraffin and preparation method thereof Download PDFInfo
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- CN105419778B CN105419778B CN201510979963.5A CN201510979963A CN105419778B CN 105419778 B CN105419778 B CN 105419778B CN 201510979963 A CN201510979963 A CN 201510979963A CN 105419778 B CN105419778 B CN 105419778B
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- Prior art keywords
- quantum dot
- silicon dioxide
- composite material
- paraffin
- dioxide layer
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 113
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 167
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 85
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 63
- 239000002077 nanosphere Substances 0.000 claims abstract description 33
- 238000001338 self-assembly Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 229910000077 silane Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- -1 sucrose ester Chemical class 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910004613 CdTe Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 claims description 4
- 229960000776 sodium tetradecyl sulfate Drugs 0.000 claims description 3
- AQQPJNOXVZFTGE-UHFFFAOYSA-N 2-octadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O AQQPJNOXVZFTGE-UHFFFAOYSA-N 0.000 claims description 2
- 229910004262 HgTe Inorganic materials 0.000 claims description 2
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 2
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000011521 glass Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000284 extract Substances 0.000 description 8
- 230000007704 transition Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 241001411320 Eriogonum inflatum Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000011806 microball Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
-
- 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
-
- 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
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
-
- 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
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
Abstract
The invention discloses a kind of quantum dot composite material containing paraffin and preparation method thereof.The quantum dot composite material includes translucency matrix, quantum dot and silicon dioxide nanosphere, and on the surface of the silicon dioxide nanosphere, the silicon dioxide nanosphere includes shell and kernel for the quantum dot self assembly, and the shell is SiO2, the kernel is paraffin.The quantum dot composite material of the present invention, the quanta point material of the present invention is not only able to keep the excellent properties such as general quantum dot luminous efficiency height, photochemical stability, and luminous intensity also has specific temperature sensitivity value, is associated or monitors available for specific temperature.The quantum dot composite material of the present invention also has good reusability, and quantum dot will not fall off problem.
Description
Technical field
It is compound more specifically to a kind of quantum dot containing paraffin the present invention relates to a kind of quantum dot composite material
Material and preparation method thereof.
Background technology
When scantling is reduced to nanometer scale, due to its nano effect, material will produce many novel and uniqueness
Better than the various functions characteristic of traditional material, valency is had a wide range of applications in fields such as microelectronics, bioengineering, chemical industry, medical science
Value.
In recent years, the nano luminescent material using transition metal as active ions, due to its excellent optical characteristics, such as absorb
Wavelength is wide and continuous, and fluorescence emission peak is tunable, fluorescence lifetime length etc., in luminescent device, fluorescence imaging, solar cell, glimmering
Light detects shows wide application prospect with fields such as biomarkers.But when quantum dot is used for luminescent device or fluoroscopic examination
When, in the range of 25-100 DEG C, the red shift that quantum dot absworption peak wavelength and photoluminescence spectra wavelength occur is generally individually smaller than
10nm.Furthermore although luminous intensity has certain linear relationship with temperature, varying with temperature, its luminous intensity is very small,
At a temperature of less than thermal quenching, less temperature change will not cause luminous intensity significantly to strengthen or weaken.Therefore, prior art
The very high quantum dot of temperature sensitivity can not be prepared.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of temperature sensitivity it is very high contain stone
The quantum dot composite material of wax.
A kind of quantum dot composite material containing paraffin provided by the invention, it includes translucency matrix, silicon dioxide layer
And quantum dot layer, the silicon dioxide layer are located in the translucency matrix, the quantum dot layer is located at the silicon dioxide layer
On, the silicon dioxide layer is formed by silicon dioxide nanosphere self assembly, the quantum dot layer by quantum dot self assembly and
Formed, the silicon dioxide nanosphere includes shell and kernel, and the shell is SiO2, the kernel is paraffin.
The quantum dot is the quantum dot of mercaptan carboxylic acid's modification；Triamido is passed through on the surface of the silicon dioxide nanosphere
Silane and aluminium polychloride modification, wherein, the chemical formula of triamido silane is H2N-CH2-CH2-NH-CH2-CH2-NH-
(CH2)3-Si-(OCH3)3。
In the quantum dot composite material, the SiO2Part by weight with the paraffin is (0.2~1.2)：1.
The quantum dot can use quantum dot commonly used in the art.The quantum dot be CdTe, CdSe, InP,
One kind in InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot
It is or several.The particle diameter of quantum dot can be 1-100nm, preferably 2-20nm, but be not restricted to this.
The silicon dioxide layer thickness is 50nm~600nm, preferably 60nm~500nm, and the quantum dot layer thickness is 2
~150nm, preferably 5~100nm；The average grain diameter of the silicon dioxide nanosphere is 50nm~600nm, preferably 60nm
~500nm.
Paraffin is preferably 18#Paraffin, 20#Paraffin, 25#Paraffin, 30#Paraffin, 35#Paraffin, 45#Paraffin, 58#One in paraffin
Kind is a variety of.
The preparation method for the above-mentioned quantum dot composite material containing paraffin that the present invention also provides, this method include following step
Suddenly：
(1) paraffin and surfactant being added in ethanol water, then heating makes paraffin melt and stir,
The emulsion containing paraffin is made, then adds tetraethyl orthosilicate in the emulsion, add aqueous slkali regulation pH to 9~
12, be then hydrolyzed reaction, stirring, stand, filtering, washing, dry after, that is, obtain the titanium dioxide of coated with silica paraffin
Silicon nanoparticle；
(2) silicon dioxide nanosphere is added to the water, ultrasonic vibration 30min, obtains silicon dioxide nanosphere
Dispersion liquid, by translucency matrix be inserted perpendicularly into for prepare silicon dioxide nanosphere dispersion liquid in carry out vertical-growth,
Drying is taken out, the silicon dioxide layer for being covered in translucency stromal surface is made；
(3) the translucency matrix that will be covered with silicon dioxide layer is disposed vertically in the aqueous solution of quantum dot, takes out drying,
Just quantum dot composite material is obtained.
In (1) step, the paraffin, surfactant and ethanol water part by weight are 10：(0.1~3.0)：
(20~100), the weight of ethanol and water ratio is (1~5) in the ethanol water:1；The weight of the paraffin and tetraethyl orthosilicate
Amount ratio is 10：(5~40).
The surfactant is polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, dodecyl sulphate
One or more in sodium, sodium tetradecyl sulfate, sodium hexadecyl sulfate, preferably lauryl sodium sulfate and/or 14
Sodium alkyl sulfate.
In (2) step, the aqueous solution of the quantum dot is the aqueous solution of the quantum dot of mercaptan carboxylic acid's modification.The immersion
Time be 5min~240min.
Before the silicon dioxide nanosphere is added into the aqueous solution of quantum dot, with polymeric aluminum chlorides solution and three
Amino silane solution modification handles silicon dioxide nanosphere, comprises the following steps that：It will be covered with the translucency of silicon dioxide layer
Matrix is positioned in the solution of aluminium polychloride, then takes out drying, is then then added in triamido solution of silane, Ran Houqu
Go out drying.Wherein, concentration 0.20wt%~0.01wt% of polymeric aluminum chlorides solution.The triamido solution of silane be containing
The ethanol solution of 0.5wt%~2.0wt% triamido silane.The dosage of polymeric aluminum chlorides solution and triamido solution of silane submerges
Titanium dioxide silication nanoparticle, but it is not restricted to this.Silicon dioxide nanosphere and polymeric aluminum chlorides solution mass ratio
Can be 1：(5~20).Silicon dioxide nanosphere can be 1 with triamido solution of silane mass ratio：(5~20).
The aqueous solution of the quantum dot is the water-soluble quantum dot of mercaptan carboxylic acid's modification, and its preparation method is as follows：By tellurium powder
Mixed with sodium borohydride with water, inert ambient environment and constant temperature are reacted, quantum dot precursor liquid is made；By caddy
It is dissolved in water, then sequentially adds mercaptan carboxylic acid and sodium hydroxide solution, obtain mixed liquor, whole mixed liquor is moved into high pressure
Kettle inside liner, letting nitrogen in and deoxidizing, then the quantum dot precursor liquid is added in the mixed liquor, it is anti-to carry out hydro-thermal in autoclave
Should, obtain the water-soluble quantum dot of mercaptan carboxylic acid's modification.The tellurium powder, sodium borohydride, caddy and mercaptan carboxylic acid rub
Your ratio is 1:(20~60):(15~45):(6~15).Mercaptan carboxylic acid is preferably TGA, 2 mercaptopropionic acid and 3- sulfydryls
Propionic acid.
Compared with prior art, it is of the invention to have the following advantages that：
(1) quantum dot composite material of the invention, quantum dot of the invention are not only able to keep general quantum dot light emitting to imitate
The excellent properties such as rate height, photochemical stability, and luminous intensity also has specific temperature sensitivity value, available for specific
Temperature is associated or monitored.It is embodied in：When the phase transition temperature of environment temperature rise paraffin, in quantum dot composite material
Paraffin undergo phase transition, transparent liquid is become by lighttight solid-state, the translucency of such silicon dioxide nanosphere is significantly
Increase, it can occur significantly to increase through the intensity (luminous intensity) of transparent base material and the photoluminescence spectra of silicon dioxide layer
Add；When environment temperature is less than the phase transition temperature of paraffin, lighttight solid-state is become by transparent liquid, such silica is received
Meter Wei Qiu translucency is greatly reduced, and it is (luminous through the intensity of transparent base material and the photoluminescence spectra of silicon dioxide layer
Intensity) it can decline to a great extent.Therefore, quantum dot composite material has very strong temperature quick near wax phase change temperature spot
Perception.
, can be by on-line real time monitoring integral system when the quantum dot composite material of the present invention is applied to fluoroscopic examination
The place of anomalous variation occurs for fluorescence, can detect the temperature minor variations near temperature sensitivity value.When for quantum dot
, can be by adjusting temperature value, to regulate and control the significantly change of quantum dot light emitting intensity during device.
The quantum dot composite material of the present invention is applied to the close sample monitoring with the phase transformation temperature pointses of paraffin, due to stone
Wax has the unusual multi-temperature trade mark, can be by selecting the paraffin of the different temperatures trade mark, to change stone in quantum dot composite material
The temperature sensitivity value of wax, so as to which the real-time monitoring of different samples can be realized.
(2) present invention is in the preparation process of quantum dot composite material, in the paraffin wax emulsion containing surfactant,
When tetraethyl orthosilicate is hydrolyzed in alkaline environment, silica is in the superficial growth of emulsion droplet, obtained silica
Nanoparticle has the SiO that neat appearance, surface flatness are higher and surface silanol group is very more2Shell, then SiO2Shell
Aggregated aluminium chloride and triamido solution of silane processing again, so as to improved silica surface charge, and in triamido silane
Polyamino and mercaptan carboxylic acid combine to form more sites of three-dimensional and be grafted, the dual work being so grafted in surface charge and more sites
Under, quantum dot is very strongly assembled in titanium dioxide nanometer layer, can effectively prevent quantum dot surface sulfydryl class part
Come off, quantum dot originally has an extraordinary time stability, and acid, alkaline stability and resists in certain acid, alkali, oxidation environment
Oxidation stability, the good bio-compatibility of quantum dot is at the same time also maintained, so as to substantially increase quantum dot specific
Stability in.
(3) quantum dot composite material of the invention, can be used in quantum dot in luminescent device, fluorescence imaging, solar energy
Battery, fluoroscopic examination and biomarker etc..
Embodiment
Below by embodiment come further illustrate the present invention quantum dot composite material preparation process, but it is not considered that
Present invention is limited only by following embodiment, wherein wt% is mass fraction.
The preparation method of the quantum dot solution of mercaptan carboxylic acid's modification uses preparation method commonly used in the art.The present invention
By the metal salt containing quantum dot cation, (cation for example can be Zn2+、Cd2+Or Hg2+) positive with mercaptan carboxylic acid's complexing generation
Ion precursor, then (anion for example can be S with anion precursor2-、Se2-Or Te2-) be heated to reflux so that quantum dot into
Core simultaneously grows, so as to which the quantum dot solution of mercaptan carboxylic acid's modification be made.The temperature being heated to reflux be 60~90 DEG C, the time be 3~
12h.For example, the cadmium telluride of mercaptan carboxylic acid's modification, the preparation method of CdSe quantum dots solution may be referred to CN
102786037A, the preparation method of the ZnS quantum dots solution of mercaptan carboxylic acid's modification may be referred to the A of CN 103242829.Amount
Son point can also be formed by cadmium sulfide, zinc selenide or the telluride zinc solution self-chambering that mercaptan carboxylic acid modifies.The following each reality of the present invention
Apply the preparation method that the cadmium telluride of mercaptan carboxylic acid's modification is described in detail in example.
Embodiment 1
(1) 25 that 100g phase transition temperatures are 25 DEG C are taken#It is water-soluble that paraffin and 20g lauryl sodium sulfate are added to 700g ethanol
In liquid, wherein the mass ratio of absolute ethyl alcohol and water is 4：1.Heated in 40 DEG C of water-baths, mechanical agitation 30 is divided after paraffin melting
Clock, obtain finely dispersed emulsion；In above-mentioned emulsion be added dropwise 80g tetraethyl orthosilicates, add NaOH solution adjust PH to
10, continue constant temperature stir 3 hours, at room temperature be aged, filter, washing, dry after produce silicon dioxide nanosphere.Pass through scanning
Electron micrograph, which characterizes, to be understood：Silicon dioxide nanosphere particle diameter is 80nm~110nm, and particle diameter distribution is uniform, and two
The shape matching of silica nanoparticle is regular, and surface is smooth.
(2) the ITO electro-conductive glass of printing opacity is cut into 2*1.5cm fritter, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is stand-by.The silica nanometer for weighing 1g good dispersions is micro-
Ball is placed in beaker, adds deionized water ultrasonic vibration 30min, to obtain the dispersion liquid of silicon dioxide nanosphere to 10ml.Measure
Move into two 2*2.5ml measuring cup, the stand-by electro-conductive glass of wash clean is inserted perpendicularly into wherein.55 DEG C of air dry oven
Vertical-growth 12h under reaction temperature, there is the electro-conductive glass of silicon dioxide layer so as to which self assembly be made.
(3) electro-conductive glass that self assembly has silicon dioxide layer is put into 100mL polymeric aluminum chlorides solutions, polyaluminium
Drying is taken out after the concentration 0.05wt%, 1min of aluminum solutions, it is molten that electro-conductive glass then is put into 100mL triamido silane again
Liquid, the solvent absolute ethyl alcohol of the solution, the concentration of triamido solution of silane is 0.5wt%, and the chemical formula of triamido silane is
H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3, drying is taken out after 20min, obtains being assembled with modified titanium dioxide
The electro-conductive glass of silicon layer.
(4) 2mg telluriums powder and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from bottle gas caused by reaction.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min, obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(tellurium powder, sodium borohydride, the molar ratio of caddy and TGA are 1 in cadmium chloride solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of TGA modification
The point aqueous solution.
(5) electro-conductive glass for being assembled with improved silica layer that step (3) obtains is disposed vertically and repaiied in TGA
The quantum dot aqueous solution 1h of decorations, after natural drying, repeats, 5 times repeatedly, completes five layers of quantum on photon crystal film
Point self assembly, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, the excitation wavelength of quantum dot
400nm, under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence spectrum of system is determined,
Obtain maximum fluorescence intensity.
Table 1
| 10℃ | 20℃ | 23℃ | 26℃ | 30℃ | 40℃ | |
| Maximum fluorescence intensity (a.u.) | 78 | 75 | 74 | 432 | 442 | 441 |
Embodiment 2
(1) 35 that 100g phase transition temperatures are 35 DEG C are taken#It is water-soluble that paraffin and 20g sodium tetradecyl sulfates are added to 500g ethanol
In liquid, wherein the mass ratio of absolute ethyl alcohol and water is 4：1.Heated in 50 DEG C of water-baths, mechanical agitation 30 is divided after paraffin melting
Clock, obtain finely dispersed emulsion；In above-mentioned emulsion be added dropwise 160g tetraethyl orthosilicates, add NaOH solution adjust PH to
10, continue constant temperature stir 4 hours, at room temperature be aged, filter, washing, dry after produce silicon dioxide nanosphere.Pass through scanning
Electron micrograph, which characterizes, to be understood：Silicon dioxide nanosphere particle diameter is 80nm~120nm, and particle diameter distribution is uniform, and two
The shape matching of silica nanoparticle is regular, and surface is smooth.
(2) the ITO electro-conductive glass of printing opacity is cut into 2*1.5cm fritter, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is stand-by.The silica nanometer for weighing 1g good dispersions is micro-
Ball is placed in beaker, adds deionized water ultrasonic vibration 30min, to obtain the dispersion liquid of silicon dioxide nanosphere to 10ml.Measure
Move into two 2*2.5ml measuring cup, the stand-by electro-conductive glass of wash clean is inserted perpendicularly into wherein.55 DEG C of air dry oven
Vertical-growth 12h under reaction temperature, there is the electro-conductive glass of silicon dioxide layer so as to which self assembly be made.
(3) 2mg selenium powders and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from bottle gas caused by reaction.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min, obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(selenium powder, sodium borohydride, the molar ratio of caddy and TGA are 1 in cadmium chloride solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of TGA modification
The point aqueous solution.
(4) electro-conductive glass for being assembled with silicon dioxide layer that step (2) obtains is disposed vertically in TGA modification
Quantum dot aqueous solution 1h, after natural drying, repeats, 6 times repeatedly, complete six layers of quantum dot on photon crystal film from
Assembling, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, the excitation wavelength of quantum dot
For 540nm.Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence light of system is determined
Spectrum, obtains maximum relative intensity of fluorescence.
Table 2
| 20℃ | 30℃ | 33℃ | 36℃ | 40℃ | 50℃ | |
| Maximum fluorescence intensity (a.u.) | 67 | 65 | 74 | 402 | 413 | 416 |
Embodiment 3
(1) 58 that 100g phase transition temperatures are 58 DEG C are taken#It is water-soluble that paraffin and 30g lauryl sodium sulfate are added to 900g ethanol
In liquid, wherein the mass ratio of absolute ethyl alcohol and water is 3：1.Heated in 65 DEG C of water-baths, mechanical agitation 30 is divided after paraffin melting
Clock, obtain finely dispersed emulsion；In above-mentioned emulsion be added dropwise 240g tetraethyl orthosilicates, add NaOH solution adjust PH to
10, continue constant temperature stir 4 hours, at room temperature be aged, filter, washing, dry after produce silicon dioxide nanosphere.Silica
Nanoparticle particle diameter is 80nm~140nm, and distribution is more uniform.
(2) the ITO electro-conductive glass of printing opacity is cut into 2*1.5cm fritter, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is stand-by.The silica nanometer for weighing 1g good dispersions is micro-
Ball is placed in beaker, adds deionized water ultrasonic vibration 30min, to obtain the dispersion liquid of silicon dioxide nanosphere to 10ml.Measure
Move into two 2*2.5ml measuring cup, the stand-by electro-conductive glass of wash clean is inserted perpendicularly into wherein.55 DEG C of air dry oven
Vertical-growth 12h under reaction temperature, there is the electro-conductive glass of silicon dioxide layer so as to which self assembly be made.
(3) electro-conductive glass that self assembly has silicon dioxide layer is positioned in 100mL polymeric aluminum chlorides solutions, polyaluminium
Drying is taken out after the concentration 0.08wt%, 1min of aluminum solutions, it is molten that electro-conductive glass then is put into 100mL triamido silane again
Liquid, the solvent absolute ethyl alcohol of the solution, the concentration of triamido solution of silane is 0.6wt%, and the chemical formula of triamido silane is
H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3, drying is taken out after 20min, obtains being assembled with modified titanium dioxide
The electro-conductive glass of silicon layer.
(4) 2mg selenium powders and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from bottle gas caused by reaction.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple.
100mg zinc nitrates are added in 100mL water, and glass bar is stirred to zinc nitrate particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min, obtains mixed liquor.
Good seal removes the zinc nitrate solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(selenium powder, sodium borohydride, the molar ratio of zinc nitrate and TGA are 1 in zinc nitrate solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of TGA modification
The point aqueous solution.
(5) electro-conductive glass for being assembled with improved silica layer that step (3) obtains is disposed vertically and repaiied in TGA
The quantum dot aqueous solution 1h of decorations, after natural drying, repeats, 5 times repeatedly, completes five layers of quantum on photon crystal film
Point self assembly, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, the excitation wavelength of quantum dot
For 470nm.Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence light of system is determined
Spectrum, obtains maximum relative intensity of fluorescence.
Table 3
| 40℃ | 50℃ | 56℃ | 59℃ | 65℃ | 70℃ | |
| Maximum fluorescence intensity (a.u.) | 59 | 53 | 66 | 370 | 387 | 389 |
Comparative example 1
(1) 20g lauryl sodium sulfate is taken to be added in 700g ethanol waters, wherein the mass ratio of absolute ethyl alcohol and water
For 4：1.Heated in 50 DEG C of water-baths, mechanical agitation 30 minutes, 80g tetraethyl orthosilicates are then added dropwise again, added NaOH solution and adjust
Save PH to 10, continue constant temperature stir 3 hours, at room temperature be aged, filter, washing, dry after produce silicon dioxide nanosphere.It is logical
Electron micrograph sign is over-scanned to understand：Silicon dioxide nanosphere particle diameter is 80nm~110nm.
(2) the ITO electro-conductive glass of printing opacity is cut into 2*1.5cm fritter, the fritter electro-conductive glass cut is respectively placed in dilute
Hydrochloric acid, absolute ethyl alcohol, deionized water are respectively cleaned by ultrasonic 15min, and drying is stand-by.The silica nanometer for weighing 1g good dispersions is micro-
Ball is placed in beaker, adds deionized water ultrasonic vibration 30min, to obtain the dispersion liquid of silicon dioxide nanosphere to 10ml.Measure
Move into two 2*2.5ml measuring cup, the stand-by electro-conductive glass of wash clean is inserted perpendicularly into wherein.55 DEG C of air dry oven
Vertical-growth 12h under reaction temperature, there is the electro-conductive glass of silicon dioxide layer so as to which self assembly be made.
(3) 2mg telluriums powder and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from bottle gas caused by reaction.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min, obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(tellurium powder, sodium borohydride, the molar ratio of caddy and TGA are 1 in cadmium chloride solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of TGA modification
The point aqueous solution.
(4) electro-conductive glass for being assembled with silicon dioxide layer that step (2) obtains is disposed vertically in TGA modification
Quantum dot aqueous solution 1h, after natural drying, repeats, 5 times repeatedly, complete five layers of quantum dot on photon crystal film from
Assembling, so as to form quantum dot composite material.
(6) using the quantum dot composite material under sepectrophotofluorometer detection different temperatures, using fluorescence spectrophotometry
Mixed solution system under meter detection different temperatures, the excitation wavelength 400nm of quantum dot, sepectrophotofluorometer is incident and is emitted
Under conditions of slit spectral band-width is 5nm, the fluorescence spectrum of system is determined, obtains maximum fluorescence intensity.
Table 4
| 10℃ | 20℃ | 23℃ | 26℃ | 30℃ | 40℃ | |
| Maximum fluorescence intensity (a.u.) | 491 | 488 | 488 | 487 | 484 | 481 |
Pass through table 1-3 data：Once the environment temperature of the composite quantum dot microballoon of each embodiment is slightly above paraffin
Phase transition temperature, the paraffin in quantum dot composite material has occurred and that phase transformation, becomes transparent liquid by lighttight solid-state, this
The translucency of sample quantum dot composite material is significantly increased, and the intensity (luminous intensity) of its photoluminescence spectra can occur significantly to increase
Add, such quantum dot, which is compounded in phase transformation temperature pointses annex, has very strong temperature sensitivity.And the composite quantum dot of comparative example 1
For the environment temperature of microballoon in elevation process, fluorescence intensity change is very small, under the influence of fluorescent noise, is unfavorable for instrument progress
Monitoring, temperature sensitivity are poor.
Test case 1
It is molten containing 0.5 μ g/L copper ions that embodiment 1-3 and the quantum dot composite material of comparative example 1 are reused into test
Liquid.As a result show：After embodiment 1-3 quantum dot composite material uses 10 times, fluorescence can return to original more than 96%,
There is not quantum dot to come off problem；And the quantum dot composite material of comparative example 1, after using 5 times, fluorescence drops to original
90%, drop to less than 80% using fluorescence after 8 times, and there is quantum dot obscission, after using 12 times, occur serious de-
Fall problem, it is impossible to be further continued for using.
Claims (12)
1. a kind of quantum dot composite material containing paraffin, it is characterised in that it includes translucency matrix, silicon dioxide layer and amount
Son point layer, the silicon dioxide layer are located in the translucency matrix, and the quantum dot layer is located in the silicon dioxide layer, institute
Silicon dioxide layer to be stated to be formed by silicon dioxide nanosphere self assembly, the quantum dot layer is formed by quantum dot self assembly,
The silicon dioxide nanosphere includes shell and kernel, and the shell is SiO2, the kernel is paraffin.
2. according to the quantum dot composite material described in claim 1, it is characterised in that：The surface of the silicon dioxide layer passes through three
Amino silane and aluminium polychloride modification, the chemical formula of the triamido silane is H2N-CH2-CH2-NH-CH2-CH2-NH-
(CH2)3-Si-(OCH3)3。
3. according to the quantum dot composite material described in claim 1 or 2, it is characterised in that：In the quantum dot composite material,
The SiO2Part by weight with the paraffin is (0.2~1.2)：1.
4. according to the quantum dot composite material described in claim 1 or 2, it is characterised in that：The silicon dioxide layer thickness is
50nm~600nm, the quantum dot layer thickness are 2~150nm；The average grain diameter of the silicon dioxide nanosphere be 50nm~
600nm。
5. according to the quantum dot composite material described in claim 4, it is characterised in that：The silicon dioxide layer thickness be 60nm~
500nm, the quantum dot layer thickness are 5~100nm；The average grain diameter of the silicon dioxide nanosphere is 60nm~500nm.
6. according to the quantum dot composite material described in claim 1 or 2, it is characterised in that：The quantum dot be CdTe, CdSe,
In InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot
It is one or more of.
7. a kind of preparation method of the quantum dot composite material containing paraffin in 1-6 such as claim as described in any one, its
It is characterised by, this method comprises the following steps：
(1) paraffin and surfactant are added in ethanol water, then heating makes paraffin melt and stir, and is made
Emulsion containing paraffin, tetraethyl orthosilicate is then added in the emulsion, add aqueous slkali regulation pH to 9~12, so
After be hydrolyzed reaction, stirring, stand, filtering, washing, dry after, that is, the silica for obtaining coated with silica paraffin is received
Meter Wei Qiu；
(2) silicon dioxide nanosphere is added to the water, ultrasonic vibration 30min, obtains point of silicon dioxide nanosphere
Dispersion liquid, by translucency matrix be inserted perpendicularly into for prepare silicon dioxide nanosphere dispersion liquid in carry out vertical-growth, take out
Dry, the silicon dioxide layer for being covered in the translucency stromal surface is made；
(3) the translucency matrix that will be covered with silicon dioxide layer is disposed vertically in the aqueous solution of quantum dot, takes out drying, just
To quantum dot composite material.
8. in accordance with the method for claim 7, it is characterised in that：The paraffin, surfactant and ethanol water weight
Ratio is 10：(0.1~3.0)：(20~100), the weight of ethanol and water ratio is (1~5) in the ethanol water:1；It is described
The part by weight of paraffin and tetraethyl orthosilicate is 10：(5~40), the surfactant are polyethylene glycol, sucrose ester, poly- sorb
One or more in ester, octadecyl benzenesulfonic acid, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate.
9. in accordance with the method for claim 8, it is characterised in that：The surfactant be lauryl sodium sulfate and/or
Sodium tetradecyl sulfate.
10. according to the method described in any one in claim 7-9, it is characterised in that：The aqueous solution of the quantum dot is mercapto
The aqueous solution of the quantum dot of yl carboxylic acid modification.
11. according to the method described in any one in claim 7-9, it is characterised in that：It will be covered with silicon dioxide layer
Translucency matrix is disposed vertically before the aqueous solution of quantum dot, at polymeric aluminum chlorides solution and triamido solution of silane modification
Silicon dioxide layer is managed, is comprised the following steps that：The translucency matrix that will be covered with silicon dioxide layer is positioned over the molten of aluminium polychloride
In liquid, drying is then taken out, is then positioned over again in triamido solution of silane, then takes out drying.
12. in accordance with the method for claim 11, it is characterised in that：The concentration 0.20wt% of the polymeric aluminum chlorides solution~
0.01wt%, the triamido solution of silane are the ethanol solution containing 0.5wt%~2.0wt% triamido silane.
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