CN105419778A - Quantum dot composite material containing paraffin and preparation method thereof - Google Patents
Quantum dot composite material containing paraffin and preparation method thereof Download PDFInfo
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- CN105419778A CN105419778A CN201510979963.5A CN201510979963A CN105419778A CN 105419778 A CN105419778 A CN 105419778A CN 201510979963 A CN201510979963 A CN 201510979963A CN 105419778 A CN105419778 A CN 105419778A
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- quantum dot
- silicon dioxide
- composite material
- solution
- paraffin
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 117
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 160
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 79
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 72
- 239000002077 nanosphere Substances 0.000 claims abstract description 41
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- -1 polyoxyethylene Polymers 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 230000005540 biological transmission Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001338 self-assembly Methods 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 9
- DDSWIYVVHBOISO-UHFFFAOYSA-N ctk0i1982 Chemical compound N[SiH](N)N DDSWIYVVHBOISO-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 claims description 5
- 229910004613 CdTe Inorganic materials 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 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
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 2
- 229950008882 polysorbate Drugs 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-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
- 238000012544 monitoring process Methods 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 52
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 34
- 239000011521 glass Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 17
- 239000002243 precursor Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 229960000935 dehydrated alcohol Drugs 0.000 description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 description 10
- 239000012279 sodium borohydride Substances 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 241001411320 Eriogonum inflatum Species 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000284 extract Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 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
- 238000001914 filtration Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 235000011194 food seasoning agent Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001000 micrograph Methods 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
- 239000002253 acid Substances 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
- 238000009826 distribution Methods 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000011701 zinc Substances 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
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000001993 wax 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Composite Materials (AREA)
- Optics & Photonics (AREA)
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- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a quantum dot composite material containing paraffin and a preparation method thereof. The quantum dot composite material includes a light-transmitting substrate, quantum dots and silicon dioxide nanospheres. The quantum dots are self-assembled on the surfaces of the silicon dioxide nanospheres. Each silicon dioxide nanosphere includes a shell layer being SiO2 and an inner core being the paraffin. The quantum dot composite material maintains the excellent characters of high luminescence efficiency, high photo-chemical stability and the like. The luminescence intensity of the composite material is relative to a special temperature sensitive value, so that the composite material can be used for correlating or monitoring special temperature. The composite material is excellent in reusability and the quantum dots are free from falling off.
Description
Technical field
The present invention relates to a kind of quantum dot composite material, more particularly, relate to a kind of quantum dot composite material containing paraffin and preparation method thereof.
Background technology
When scantling reduces to nanometer scale, due to its nano effect, material, by producing the various functional performances being better than traditional material of many novelties and uniqueness, is with a wide range of applications in fields such as microelectronics, biotechnology, chemical industry, medical science.
In recent years, take transition metal as the nano luminescent material of active ions, due to the optical characteristics of its excellence, as wide in absorbing wavelength and continuously, fluorescence emission peak is tunable, fluorescence lifetime is long, shows wide application prospect in fields such as luminescent device, fluorescence imaging, solar cell, fluoroscopic examination and biomarkers.But when quantum dot is used for luminescent device or fluoroscopic examination, within the scope of 25-100 DEG C, the red shift that quantum dot absorption peak wavelength and photoluminescence spectra wavelength occur generally all is less than 10nm.Moreover although luminous intensity and temperature have certain linear relationship, vary with temperature, its luminous intensity is very little, lower than at thermal quenching temperature, less temperature variation can not cause luminous intensity significantly strengthen or weaken.Therefore, prior art can not prepare the very high quantum dot of temperature sensitivity.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides the quantum dot composite material containing paraffin that a kind of temperature sensitivity is very high.
A kind of quantum dot composite material containing paraffin provided by the invention, it comprises light transmission matrix, silicon dioxide layer and quantum dot layer, described silicon dioxide layer is positioned in described light transmission matrix, described quantum dot layer is positioned on described silicon dioxide layer, described silicon dioxide layer is formed by silicon dioxide nanosphere self-assembly, described quantum dot layer is formed by quantum dot self-assembly, and described silicon dioxide nanosphere comprises shell and kernel, and described shell is SiO
2, described kernel is paraffin.
Described quantum dot is the quantum dot that mercaptan carboxylic acid modifies; The surface of described silicon dioxide nanosphere is through triamino silane and polymerize aluminum chloride modification, and wherein, the chemical formula of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3.
In described quantum dot composite material, described SiO
2be (0.2 ~ 1.2) with the part by weight of described paraffin: 1.
The quantum dot that described quantum dot can adopt this area routine to use.Described quantum dot is one or more in CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot.The particle diameter of quantum dot can be 1-100nm, is preferably 2-20nm, but is not restricted to this.
Described silicon dioxide layer thickness is 50nm ~ 600nm, and be preferably 60nm ~ 500nm, described quantum dot layer thickness is 2 ~ 150nm, is preferably 5 ~ 100nm; The median size of described silicon dioxide nanosphere is 50nm ~ 600nm, is preferably 60nm ~ 500nm.
Paraffin is preferably 18
#paraffin, 20
#paraffin, 25
#paraffin, 30
#paraffin, 35
#paraffin, 45
#paraffin, 58
#one or more in paraffin.
The preparation method of the above-mentioned quantum dot composite material containing paraffin that the present invention also provides, the method comprises the steps:
(1) paraffin and tensio-active agent are joined in aqueous ethanolic solution, then heating makes paraffin melting and stirs, the obtained emulsion containing paraffin, then in described emulsion, tetraethoxy is added, add alkaline solution and regulate pH to 9 ~ 12, then be hydrolyzed reaction, stirs, leaves standstill, filters, washing, after drying, namely obtains the silicon dioxide nanosphere of coated with silica paraffin;
(2) described silicon dioxide nanosphere is added to the water, ultrasonic vibration 30min, obtain the dispersion liquid of silicon dioxide nanosphere, light transmission matrix is vertically inserted in the dispersion liquid for the preparation of silicon dioxide nanosphere and carry out vertical-growth, take out dry, the obtained silicon dioxide layer being covered in light transmission stromal surface;
(3) the light transmission matrix being coated with silicon dioxide layer is vertically positioned in the aqueous solution of quantum dot, takes out dry, just obtain quantum dot composite material.
In (1) step, described paraffin, tensio-active agent and aqueous ethanolic solution part by weight are 10:(0.1 ~ 3.0): (20 ~ 100), in described aqueous ethanolic solution, the weight ratio of ethanol and water is (1 ~ 5): 1; The part by weight of described paraffin and tetraethoxy is 10:(5 ~ 40).
Described tensio-active agent is one or more in polyoxyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, sodium lauryl sulphate, Trombovar, Sodium palmityl sulfate, is preferably sodium lauryl sulphate and/or Trombovar.
In (2) step, the aqueous solution of described quantum dot is the aqueous solution of the quantum dot that mercaptan carboxylic acid modifies.The time of described immersion is 5min ~ 240min.
Before the aqueous solution described silicon dioxide nanosphere being joined quantum dot, with polymeric aluminum chlorides solution and triamino solution of silane modification silicon dioxide nanosphere, concrete steps are as follows: be positioned in the solution of polymerize aluminum chloride by the light transmission matrix being coated with silicon dioxide layer, then drying is taken out, and then join in triamino solution of silane, then take out drying.Wherein, the concentration 0.20wt% ~ 0.01wt% of polymeric aluminum chlorides solution.Described triamino solution of silane is the ethanolic soln containing 0.5wt% ~ 2.0wt% triamino silane.The consumption submergence titanium dioxide silication Nano microsphere of polymeric aluminum chlorides solution and triamino solution of silane, but be not restricted to this.Silicon dioxide nanosphere and polymeric aluminum chlorides solution mass ratio can be 1:(5 ~ 20).Silicon dioxide nanosphere and triamino solution of silane mass ratio can be 1:(5 ~ 20).
The aqueous solution of described quantum dot is the water-soluble quantum dot that mercaptan carboxylic acid modifies, and its preparation method is as follows: tellurium powder and sodium borohydride are mixed with water, inert ambient environment and constant temperature is reacted, obtained quantum dot precursor liquid; Cadmium chloride fine powder is dissolved in water, then mercaptan carboxylic acid and sodium hydroxide solution is added successively, obtain mixed solution, whole mixed solution is moved to autoclave inside liner, letting nitrogen in and deoxidizing, then described quantum dot precursor liquid is joined in described mixed solution, carry out hydro-thermal reaction at autoclave, obtain the water-soluble quantum dot that described mercaptan carboxylic acid modifies.The molar ratio of described tellurium powder, sodium borohydride, Cadmium chloride fine powder and mercaptan carboxylic acid is 1:(20 ~ 60): (15 ~ 45): (6 ~ 15).Mercaptan carboxylic acid is preferably Thiovanic acid, 2 mercaptopropionic acid and 3-thiohydracrylic acid.
Compared with prior art, tool of the present invention has the following advantages:
(1) quantum dot composite material of the present invention, quantum dot of the present invention not only can keep the excellent properties such as general quantum dot luminous efficiency is high, photochemical stability, and luminous intensity also has specific temperature sensitive value, can be used for associating specific temperature or monitoring.Be embodied in: when envrionment temperature raises the transformation temperature of paraffin, paraffin in quantum dot composite material undergoes phase transition, solid-stately transparent liquid state is become by lighttight, the light transmission of such silicon dioxide nanosphere significantly increases, and its intensity (luminous intensity) of passing the photoluminescence spectra of transparent base material and silicon dioxide layer can occur significantly to increase; When the transformation temperature of envrionment temperature lower than paraffin, become lighttight solid-state by transparent liquid state, the light transmission of such silicon dioxide nanosphere significantly reduces, and its intensity (luminous intensity) of passing the photoluminescence spectra of transparent base material and silicon dioxide layer can decline to a great extent.Therefore, quantum dot composite material has very strong temperature sensitivity near wax phase change temperature spot.
When quantum dot composite material of the present invention is applied to fluoroscopic examination, by the place of fluorescence generation ANOMALOUS VARIATIONS in on-line real time monitoring integral system, the temperature subtle change near temperature sensitive value can be monitored out.When device for quantum dot, by regulating temperature value, the significantly change of quantum dot light emitting intensity can be regulated and controled.
Quantum dot composite material of the present invention is applicable to the close sample monitoring with the phase transformation temperature points of paraffin, because paraffin has very many temperature trade mark, can by selecting the paraffin of the differing temps trade mark, change the temperature sensitive value of paraffin in quantum dot composite material, thus the Real-Time Monitoring of different sample can be realized.
(2) the present invention is in the preparation process of quantum dot composite material, containing in the paraffin wax emulsion of tensio-active agent, when tetraethoxy is hydrolyzed in alkaline environment, silicon-dioxide is in the surface growth of emulsion droplet, and the silicon dioxide nanosphere obtained has the SiO that neat appearance, surface flatness are higher and surface silanol group is very many
2shell, then SiO
2shell is again through polymerize aluminum chloride and the process of triamino solution of silane, thus improved silica surface charge, and be combined at the polyamino of triamino silane the multidigit point grafting forming three-dimensional with mercaptan carboxylic acid, like this under the dual function of surface charge and the grafting of multidigit point, quantum dot is assembled in titanium dioxide nanometer layer very securely, can effectively prevent coming off of quantum dot surface sulfydryl class part, quantum dot originally has extraordinary time stability, and in certain acid, alkali, acid in well-oxygenated environment, alkaline stability and antioxidative stabilizer, meanwhile also maintain the good bio-compatibility of quantum dot, thus substantially increase quantum dot stability in a particular application.
(3) quantum dot composite material of the present invention, may be used at quantum dot in luminescent device, fluorescence imaging, solar cell, fluoroscopic examination and biomarker etc.
Embodiment
Further illustrate the preparation process of quantum dot composite material of the present invention below by embodiment, but invention should not be deemed limited in following embodiment, wherein wt% is massfraction.
The preparation method of the quantum dot solution that mercaptan carboxylic acid modifies adopts the preparation method of this area routine use.The present invention will (cat ions be as being Zn containing the cationic metal-salt of quantum dot
2+, Cd
2+or Hg
2+) generate positively charged ion precursor with mercaptan carboxylic acid's complexing, then (negatively charged ion can be such as S with negatively charged ion precursor
2-, Se
2-or Te
2-) reflux makes quantum dot nucleation and grows, thus the quantum dot solution that obtained mercaptan carboxylic acid modifies.The temperature of reflux is 60 ~ 90 DEG C, and the time is 3 ~ 12h.Such as, the cadmium telluride that mercaptan carboxylic acid modifies, the preparation method of CdSe quantum dots solution can with reference to CN102786037A, and the preparation method of the ZnS quantum dots solution that mercaptan carboxylic acid modifies can with reference to CN103242829A.Cadmium Sulfide, zinc selenide or the self-chambering of zinc telluridse solution that quantum dot can also be modified by mercaptan carboxylic acid form.The preparation method of the cadmium telluride of each embodiment detailed description mercaptan carboxylic acid modification that the present invention is following.
Embodiment 1
(1) get that 100g transformation temperature is 25 DEG C 25
#paraffin and 20g sodium lauryl sulphate join in 700g aqueous ethanolic solution, and wherein the mass ratio of dehydrated alcohol and water is 4:1.Heat in 40 DEG C of water-baths, after paraffin melting, mechanical stirring 30 minutes, obtains finely dispersed emulsion; In above-mentioned emulsion, drip 80g tetraethoxy, add NaOH solution and regulate PH to 10, continue constant temperature and stir 3 hours, after ageing under room temperature, filtration, washing, drying, namely obtain silicon dioxide nanosphere.Characterized known by electron scanning micrograph: silicon dioxide nanosphere particle diameter is 80nm ~ 110nm, even particle size distribution, and the shape matching of silicon dioxide nanosphere is regular, smooth surface.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The silicon dioxide nanosphere taking 1g good dispersity is placed in beaker, adds deionized water to 10ml, and ultrasonic vibration 30min obtains the dispersion liquid of silicon dioxide nanosphere.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of silicon dioxide layer.
(3) conductive glass of silicon dioxide layer self-assembly is had to put in 100mL polymeric aluminum chlorides solution, the concentration 0.05wt% of polymeric aluminum chlorides solution, take out dry after 1min, and then conductive glass is put into 100mL triamino solution of silane, the solvent dehydrated alcohol of this solution, the concentration of triamino solution of silane is 0.5wt%, and the chemical formula of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3, take out dry after 20min, obtain the conductive glass being assembled with improved silica layer.
(4) take 2mg tellurium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of tellurium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(5) conductive glass being assembled with improved silica layer that step (3) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 5 times repeatedly, complete five layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength 400nm of quantum dot, under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, 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) get that 100g transformation temperature is 35 DEG C 35
#paraffin and 20g Trombovar join in 500g aqueous ethanolic solution, and wherein the mass ratio of dehydrated alcohol and water is 4:1.Heat in 50 DEG C of water-baths, after paraffin melting, mechanical stirring 30 minutes, obtains finely dispersed emulsion; In above-mentioned emulsion, drip 160g tetraethoxy, add NaOH solution and regulate PH to 10, continue constant temperature and stir 4 hours, after ageing under room temperature, filtration, washing, drying, namely obtain silicon dioxide nanosphere.Characterized known by electron scanning micrograph: silicon dioxide nanosphere particle diameter is 80nm ~ 120nm, even particle size distribution, and the shape matching of silicon dioxide nanosphere is regular, smooth surface.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The silicon dioxide nanosphere taking 1g good dispersity is placed in beaker, adds deionized water to 10ml, and ultrasonic vibration 30min obtains the dispersion liquid of silicon dioxide nanosphere.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of silicon dioxide layer.
(3) take 2mg selenium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of selenium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(4) conductive glass being assembled with silicon dioxide layer that step (2) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 6 times repeatedly, complete six layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength of quantum dot is 540nm.Under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, obtain 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) get that 100g transformation temperature is 58 DEG C 58
#paraffin and 30g sodium lauryl sulphate join in 900g aqueous ethanolic solution, and wherein the mass ratio of dehydrated alcohol and water is 3:1.Heat in 65 DEG C of water-baths, after paraffin melting, mechanical stirring 30 minutes, obtains finely dispersed emulsion; In above-mentioned emulsion, drip 240g tetraethoxy, add NaOH solution and regulate PH to 10, continue constant temperature and stir 4 hours, after ageing under room temperature, filtration, washing, drying, namely obtain silicon dioxide nanosphere.Silicon dioxide nanosphere particle diameter is 80nm ~ 140nm, distributes comparatively even.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The silicon dioxide nanosphere taking 1g good dispersity is placed in beaker, adds deionized water to 10ml, and ultrasonic vibration 30min obtains the dispersion liquid of silicon dioxide nanosphere.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of silicon dioxide layer.
(3) conductive glass of silicon dioxide layer self-assembly is had to be positioned in 100mL polymeric aluminum chlorides solution, the concentration 0.08wt% of polymeric aluminum chlorides solution, take out dry after 1min, and then conductive glass is put into 100mL triamino solution of silane, the solvent dehydrated alcohol of this solution, the concentration of triamino solution of silane is 0.6wt%, and the chemical formula of triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3, take out dry after 20min, obtain the conductive glass being assembled with improved silica layer.
(4) take 2mg selenium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg zinc nitrate adds in 100mL water, and glass stick is stirred to zinc nitrate particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the zinc nitrate solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of selenium powder, sodium borohydride, zinc nitrate and Thiovanic acid is 1:41:33:9) in zinc nitrate solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(5) conductive glass being assembled with improved silica layer that step (3) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 5 times repeatedly, complete five layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength of quantum dot is 470nm.Under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, measure the fluorescence spectrum of system, obtain 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) getting 20g sodium lauryl sulphate joins in 700g aqueous ethanolic solution, and wherein the mass ratio of dehydrated alcohol and water is 4:1.Heat in 50 DEG C of water-baths, mechanical stirring 30 minutes, and then drip 80g tetraethoxy, add NaOH solution and regulate PH to 10, continue constant temperature and stir 3 hours, after ageing under room temperature, filtration, washing, drying, namely obtain silicon dioxide nanosphere.Characterized known by electron scanning micrograph: silicon dioxide nanosphere particle diameter is 80nm ~ 110nm.
(2) the ITO conductive glass of printing opacity is cut into the fritter of 2*1.5cm, the fritter conductive glass cut is placed in dilute hydrochloric acid, dehydrated alcohol, each ultrasonic cleaning 15min of deionized water respectively, dries up stand-by.The silicon dioxide nanosphere taking 1g good dispersity is placed in beaker, adds deionized water to 10ml, and ultrasonic vibration 30min obtains the dispersion liquid of silicon dioxide nanosphere.Measure in the weighing bottle moving to two 2*2.5ml, conductive glass stand-by for wash clean is vertically inserted wherein.Vertical-growth 12h under air dry oven 55 DEG C of temperature of reaction, thus obtained self-assembly has the conductive glass of silicon dioxide layer.
(3) take 2mg tellurium powder and 24mg sodium borohydride, in the middle of the bottle moving to band bottle stopper, logical nitrogen 5min, builds bottle stopper.Syringe extracts high purity water 2mL, is expelled in bottle, and then discharges the gas that in bottle, reaction produces.Put in water-bath by whole small bottle packing, temperature of reaction is 32 DEG C, takes out after 2h, is prepared into the precursor liquid that purple is fresh.
100mg Cadmium chloride fine powder adds in 100mL water, and glass stick is stirred to Cadmium chloride fine powder particle and dissolves completely, and add Thiovanic acid (TGA) and more whole liquid is moved to autoclave inside liner, letting nitrogen in and deoxidizing 30min, obtains mixed solution.
Good seal is except the cadmium chloride solution of peroxide, syringe extracts the fresh precursor liquid for preparing of 1mL and is quickly moved to (molar ratio of tellurium powder, sodium borohydride, Cadmium chloride fine powder and Thiovanic acid is 1:41:33:9) in cadmium chloride solution, add sodium hydroxide solution and PH is adjusted to 10, build lid, assemble autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum dot aqueous solution that Thiovanic acid is modified.
(4) conductive glass being assembled with silicon dioxide layer that step (2) obtains vertically is positioned over the quantum dot aqueous solution 1h that Thiovanic acid is modified, after seasoning, repeat, 5 times repeatedly, complete five layers of quantum dot self-assembly on photon crystal film, thus form quantum dot composite material.
(6) quantum dot composite material under adopting spectrophotofluorometer to detect differing temps, mixed solution system under adopting spectrophotofluorometer to detect differing temps, the excitation wavelength 400nm of quantum dot, under spectrophotofluorometer incidence and exit slit spectral band-width are the condition of 5nm, the fluorescence spectrum of mensuration system, obtains maximum fluorescence intensity.
Table 4
| 10℃ | 20℃ | 23℃ | 26℃ | 30℃ | 40℃ | |
| Maximum fluorescence intensity (a.u.) | 491 | 488 | 488 | 487 | 484 | 481 |
Known by showing the data of 1-3: the envrionment temperature of the composite quantum dot microballoon of each embodiment is once a little more than the transformation temperature of paraffin, paraffin in quantum dot composite material undergoes phase transition, solid-stately transparent liquid state is become by lighttight, the light transmission of such quantum dot composite material significantly increases, the intensity (luminous intensity) of its photoluminescence spectra can occur significantly to increase, and such quantum dot is compounded in phase transformation temperature points annex and has very strong temperature sensitivity.And the envrionment temperature of the composite quantum dot microballoon of comparative example 1 is at elevation process, fluorescence intensity change is very little, and under the impact of fluorescent noise, be unfavorable for that instrument is monitored, temperature sensitivity is poor.
Test case 1
The quantum dot composite material of embodiment 1-3 and comparative example 1 is reused test containing 0.5 μ g/L copper ion solution.Result shows: after the quantum dot composite material of embodiment 1-3 uses 10 times, fluorescence can return to original more than 96%, does not occur that quantum dot comes off problem; And the quantum dot composite material of comparative example 1, after use 5 times, fluorescence drops to original 90%, and after using 8 times, fluorescence drops to less than 80%, and occurs quantum dot obscission, after use 12 times, occurs severe detachment problem, can not continue to use again.
Claims (10)
1. the quantum dot composite material containing paraffin, it is characterized in that, it comprises light transmission matrix, silicon dioxide layer and quantum dot layer, described silicon dioxide layer is positioned in described light transmission matrix, described quantum dot layer is positioned on described silicon dioxide layer, and described silicon dioxide layer is formed by silicon dioxide nanosphere self-assembly, and described quantum dot layer is formed by quantum dot self-assembly, described silicon dioxide nanosphere comprises shell and kernel, and described shell is SiO
2, described kernel is paraffin.
2. according to quantum dot composite material according to claim 1, it is characterized in that: the surface of described silicon dioxide layer is through triamino silane and polymerize aluminum chloride modification, and the chemical formula of described triamino silane is H
2n-CH
2-CH
2-NH-CH
2-CH
2-NH-(CH
2)
3-Si-(OCH
3)
3.
3. according to the quantum dot composite material described in claim 1 or 2, it is characterized in that: in described quantum dot composite material, described SiO
2be (0.2 ~ 1.2) with the part by weight of described paraffin: 1.
4. according to the quantum dot composite material described in claim 1 or 2, it is characterized in that: described silicon dioxide layer thickness is 50nm ~ 600nm, be preferably 60nm ~ 500nm, described quantum dot layer thickness is 2 ~ 150nm, is preferably 5 ~ 100nm; The median size of described silicon dioxide nanosphere is 50nm ~ 600nm, is preferably 60nm ~ 500nm.
5. according to the quantum dot composite material described in claim 1 or 2, it is characterized in that: described quantum dot is one or more in CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot.
6., as a preparation method for the quantum dot composite material containing paraffin in claim 1-5 as described in any one, it is characterized in that, the method comprises the steps:
(1) paraffin and tensio-active agent are joined in aqueous ethanolic solution, then heating makes paraffin melting and stirs, the obtained emulsion containing paraffin, then in described emulsion, tetraethoxy is added, add alkaline solution and regulate pH to 9 ~ 12, then be hydrolyzed reaction, stirs, leaves standstill, filters, washing, after drying, namely obtains the silicon dioxide nanosphere of coated with silica paraffin;
(2) described silicon dioxide nanosphere is added to the water, ultrasonic vibration 30min, obtain the dispersion liquid of silicon dioxide nanosphere, light transmission matrix is vertically inserted in the dispersion liquid for the preparation of silicon dioxide nanosphere and carry out vertical-growth, take out dry, the obtained silicon dioxide layer being covered in described light transmission stromal surface;
(3) the light transmission matrix being coated with silicon dioxide layer is vertically positioned in the aqueous solution of quantum dot, takes out dry, just obtain quantum dot composite material.
7. in accordance with the method for claim 6, it is characterized in that: described paraffin, tensio-active agent and aqueous ethanolic solution part by weight are 10:(0.1 ~ 3.0): (20 ~ 100), in described aqueous ethanolic solution, the weight ratio of ethanol and water is (1 ~ 5): 1; The part by weight of described paraffin and tetraethoxy is 10:(5 ~ 40), described tensio-active agent is one or more in polyoxyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, sodium lauryl sulphate, Trombovar, Sodium palmityl sulfate, is preferably sodium lauryl sulphate and/or Trombovar.
8. according to the method described in claim 6 or 7, it is characterized in that: the aqueous solution of described quantum dot is the aqueous solution of the quantum dot that mercaptan carboxylic acid modifies.
9. according to the method described in claim 6 or 7, it is characterized in that: before the light transmission matrix being coated with silicon dioxide layer is vertically positioned over the aqueous solution of quantum dot, with polymeric aluminum chlorides solution and triamino solution of silane modification silicon dioxide layer, concrete steps are as follows: be positioned in the solution of polymerize aluminum chloride by the light transmission matrix being coated with silicon dioxide layer, then drying is taken out, and then be positioned in triamino solution of silane, then take out drying.
10. in accordance with the method for claim 9, it is characterized in that: the concentration 0.20wt% ~ 0.01wt% of described polymeric aluminum chlorides solution, described triamino solution of silane is the ethanolic soln containing 0.5wt% ~ 2.0wt% triamino silane.
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