CN109233805A - With the antifalsification label material and its preparation method and application for bearing hot quenching effect - Google Patents
With the antifalsification label material and its preparation method and application for bearing hot quenching effect Download PDFInfo
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- CN109233805A CN109233805A CN201811065842.XA CN201811065842A CN109233805A CN 109233805 A CN109233805 A CN 109233805A CN 201811065842 A CN201811065842 A CN 201811065842A CN 109233805 A CN109233805 A CN 109233805A
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 230000000171 quenching effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 32
- 230000002708 enhancing effect Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000011258 core-shell material Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 18
- 239000002159 nanocrystal Substances 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 13
- 230000007547 defect Effects 0.000 claims description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- -1 octadecylenes Chemical class 0.000 claims description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- WFNBSLYTFHMPBY-UHFFFAOYSA-N acetic acid;erbium Chemical compound [Er].CC(O)=O WFNBSLYTFHMPBY-UHFFFAOYSA-N 0.000 claims description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 5
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 claims description 5
- OQRMRSDZEJMEHR-UHFFFAOYSA-N acetic acid;scandium Chemical compound [Sc].CC(O)=O OQRMRSDZEJMEHR-UHFFFAOYSA-N 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021266 NaErF4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- WGRULTCAYDOGQK-UHFFFAOYSA-M sodium;sodium;hydroxide Chemical compound [OH-].[Na].[Na+] WGRULTCAYDOGQK-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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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
- C09K11/02—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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to phosphor fields.With the antifalsification label material for bearing hot quenching effect, molecular formula NaGdF4@xCa/yYb/zEr:NaScF4, x is between 10-40, in xCa/yYb/zEr:NaScF4In correspond to Ca2+Doped ions concentration be 10%-40%, y is between 10-30, in xCa/yYb/zEr:NaScF4In correspond to Yb3+Doped ions concentration be 10-30%, z is between 2-10, in xCa/yYb/zEr:NaScF4In correspond to Er3+Doped ions concentration be 2-10%.The material can be under conditions of not changing nanocrystalline size, and substantially hot quenching effect is born in enhancing, i.e. luminous intensity greatly enhances with the raising of temperature.
Description
Technical field
The invention belongs to phosphor fields, are related to a kind of antifalsification label material.
Technical background
As the temperature rises, phonon increasing number is radiationless caused by phonon auxiliary for the hot quencher material of tradition
Relaxation probability increases, and active ions fluorescence intensity is caused to be gradually reduced with the raising of temperature.This result seriously hinders lanthanum
It is development of the doped luminescent material in related application field, such as at high temperature, there are large errors for optical thermometers；Temperature-independent
The variation range of colorimetric material relative spectral become limited etc..Recent research result indicate that nano material can produce by table
Hot quenching effect is born caused by planar defect, however the effect that this luminous intensity increases and enhances with temperature is not obvious enough.
Summary of the invention
It is an object of the invention to open one kind under conditions of not changing nanocrystalline size, substantially enhance negative hot-quenching and go out
Antifalsification label material of effect and its preparation method and application.
Technical scheme is as follows: having the antifalsification label material for bearing hot quenching effect, molecular formula NaGdF4@
xCa/yYb/zEr: NaScF4, x is between 10-40, in xCa/yYb/zEr:NaScF4In correspond to Ca2+Doped ions
Concentration is 10%-40%, and y is between 10-30, in xCa/yYb/zEr:NaScF4In correspond to Yb3+Doped ions concentration be
10-30%, z are between 2-10, in xCa/yYb/zEr:NaScF4In correspond to Er3+Doped ions concentration be 2-10%.Shell
Middle Ca2+ 、Yb3+ 、Er3+And Sc3+Belong to the element in matrix for 100%, Sc, its concentration is according to Ca2+ 、Yb3+ 、Er3+It mixes
Miscellaneous ratio adjusts accordingly.
Preferably, sensitized ions and active ions are limited in the shell of two-dimensional space by building core-shell structure,
And vacancy-like defects state energy capture center is introduced by lower valency ion doping, increase under conditions of not changing nanocrystalline size
Hot quenching effect is born by force, i.e. luminous intensity greatly enhances with the raising of temperature.
Preparation method with the antifalsification label material for bearing hot quenching effect, is prepared by following steps:
(1) 0.8 mM of gadolinium and 8 milliliters of oleic acid are added in the three-neck flask that capacity is 50 milliliters, in nitrogen atmosphere
Protection under, adjust the temperature to 155o30 minutes are kept the temperature after C；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to
150o30 minutes are kept the temperature after C, obtains clear solution B；After B solution naturally cools to room temperature, contain 3 mMs of fluorine for 8 milliliters
The methanol solution for changing ammonium and 2 mMs of sodium hydroxides is added dropwise in B solution, wait be warming up to 60oHalf an hour is kept the temperature after C；To
Temperature all after volatilization, is risen to 280 rapidly by methanol solutionoC naturally cools to room after keeping the temperature 90 minutes at this temperature
Temperature；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by NaGdF4It is nanocrystalline be stored in it is standby in 4ml hexamethylene
With；
(2) by 0.38-0.78 mMs of acetic acid scandium, 0.1-0.3 mMs of ytterbium acetate, 0.02-0.1 mMs of acetic acid erbium,
0.1-0.4 mMs of calcium acetate and 8 milliliters of oleic acid are added in 50 milliliters of three-neck flasks, will be warm under the protection of nitrogen atmosphere
Degree is adjusted to 150o30 minutes are kept the temperature after C；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to 150o30 points are kept the temperature after C
Clock obtains clear solution C；After C solution naturally cools to room temperature, nanocrystal solution prepared in (1) is added to three necks
In flask, it is warming up to 110o40 minutes are kept the temperature after C, obtains solution D；After hexamethylene drains, contain 3 mMs of fluorinations for 8 milliliters
The methanol solution of ammonium and 2 mMs of sodium hydroxides is added dropwise in solution D, wait be warming up to 60oHalf an hour is kept the temperature after C；To first
Temperature all after volatilization, is risen to 280 rapidly by alcoholic solutionoC naturally cools to room after keeping the temperature 120 minutes at this temperature
Temperature；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by NaGdF4@Ca/Yb/Er: NaScF4Core-shell structure
It is nanocrystalline to be placed in 40oFinal product is dried to obtain in C baking oven.
A kind of antifalsification label has the antifalsification label material for bearing hot quenching effect using above-mentioned.
The beneficial effects of the invention are that: building NaGdF4@xCa/yYb/zEr: NaScF4Core-shell structure, by sensitized ions with
Active ions are limited in the shell of two-dimensional space, and further introduce vacancy-like defects state energy by lower valency ion doping
Trap center, the material can be under conditions of not changing nanocrystalline size, and substantially hot quenching effect is born in enhancing, i.e., luminous intensity with
The raising of temperature and greatly enhance.The advantages of core-shell structure is: a, sensitized ions and active ions are limited in two-dimentional sky
Between shell in, substantially reduce active ions to surface defect energy transfer distance so that the strong light of system at room temperature
Degree substantially weakens；B, hot quenching effect is born as caused by surface defect as temperature increases, in shell to dramatically increase；C, with temperature
Degree increases, and the defect introduced by lower valency ion doping captures electronics in room temperature, and the process of high temperature release electronics further promotes
Bear hot quenching effect；Based on this, the multicolor luminous of temperature dependency abundant can be realized in conjunction with positive and negative hot quenching effect, favorably
In the development for being greatly promoted optical anti-counterfeiting label material.
Detailed description of the invention
Fig. 1: NaGdF in embodiment 14@20Ca/20Yb/2Er: NaScF4The XRD diagram of nano-crystal with core-shell structure；
Fig. 2: NaGdF in embodiment 14@20Ca/20Yb/2Er: NaScF4The TEM and EDS-mapping of nano-crystal with core-shell structure
Figure；
Fig. 3: NaGdF in embodiment 14@20Ca/20Yb/2Er: NaScF4Nano-crystal with core-shell structure is under the excitation of 980nm wavelength
Alternating temperature fluorescence spectra and its amplitude enhance tendency chart；
Fig. 4: NaGdF in embodiment 14@20Ca/20Yb/2Er: NaScF4Pattern prepared by nano-crystal with core-shell structure exists
Under the excitation of 980nm wavelength, luminous intensity variation with temperature figure；
Fig. 5: NaGdF in embodiment 14@20Ca/20Yb/2Er: NaGdF4Nano-crystal with core-shell structure and 20Yb/1Tm:NaGdF4
Prepared pattern after nanocrystalline mixing, under 980nm excitation, luminescent color and intensity vary with temperature figure；
Fig. 6: NaGdF in embodiment 24@40Ca/20Yb/2Er: NaScF4The TEM of nano-crystal with core-shell structure schemes；
Fig. 7: NaGdF in embodiment 24@40Ca/20Yb/2Er: NaScF4Nano-crystal with core-shell structure is under the excitation of 980nm wavelength
Alternating temperature fluorescence spectra and its amplitude enhance tendency chart；
Fig. 8: 20Yb/2Er:NaGdF in comparative example4Nanocrystalline TEM figure；
Fig. 9: 20Yb/2Er:NaGdF in comparative example4Nanocrystalline alternating temperature fluorescence spectra and its width under the excitation of 980nm wavelength
Degree enhancing tendency chart.
Specific embodiment
The present invention is described further with embodiment with reference to the accompanying drawings of the specification.
Embodiment 1
With the antifalsification label material for bearing hot quenching effect, molecular formula NaGdF4@20Ca/20Yb/2Er: NaScF4, pass through
Following steps are prepared:
(1) 0.8 mM of gadolinium and 8 milliliters of oleic acid are added in the three-neck flask that capacity is 50 milliliters, in nitrogen atmosphere
Protection under, adjust the temperature to 155o30 minutes are kept the temperature after C；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to
150o30 minutes are kept the temperature after C, obtains clear solution B；After B solution naturally cools to room temperature, contain 3 mMs of fluorine for 8 milliliters
The methanol solution for changing ammonium and 2 mMs of sodium hydroxides is added dropwise in B solution, wait be warming up to 60oHalf an hour is kept the temperature after C；To
Temperature all after volatilization, is risen to 280 rapidly by methanol solutionoC naturally cools to room after keeping the temperature 90 minutes at this temperature
Temperature；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by NaGdF4It is nanocrystalline be stored in it is standby in 4ml hexamethylene
With；
(2) by 0.58 mM of acetic acid scandium, 0.2 mM of ytterbium acetate, 0.02 mM of acetic acid erbium, 0.2 mM of calcium acetate
It is added in 50 milliliters of three-neck flasks with 8 milliliters of oleic acid, under the protection of nitrogen atmosphere, adjusts the temperature to 150o30 are kept the temperature after C
Minute；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to 150o30 minutes are kept the temperature after C, obtains clear solution C；
After C solution naturally cools to room temperature, nanocrystal solution prepared in (1) is added in three-neck flask, is warming up to 110oC
40 minutes are kept the temperature afterwards, obtains solution D；After hexamethylene drains, contain 3 mMs of ammonium fluorides and 2 mMs of sodium hydroxides for 8 milliliters
Methanol solution be added dropwise in solution D, wait be warming up to 60oHalf an hour is kept the temperature after C；After methanol solution all volatilization,
Temperature is risen to 280 rapidlyoC naturally cools to room temperature after keeping the temperature 120 minutes at this temperature；Ethyl alcohol is used by gained is nanocrystalline
It is washed with hexamethylene mixed liquor, finally by NaGdF4@20Ca/20Yb/2Er: NaScF4Nano-crystal with core-shell structure is placed in 40oC
Final product is dried to obtain in baking oven.
NaGdF made from technical solution of the present invention4@20Ca/20Yb/2Er: NaScF4It is nanocrystalline, as shown in Figure 1, logical
XRD analysis is crossed, obtained product is pure hexagonal phase；As shown in Fig. 2, TEM and EDS-mapping analysis and observation shows product
Pattern is monodispersed unifonn spherical, and size is about 11nm, and the sensitized ions adulterated and active ions are limited in two dimension
In the shell in space.As shown in figure 3, alternating temperature spectrofluorimetry structure shows and as temperature from 293K is increased to 413K,
NaGdF4@20Ca/20Yb/2Er: NaScF4The Up-conversion Intensity of nano-crystal with core-shell structure enhances about 10.9 times.This be by
In the shell that sensitized ions and active ions are restricted to two-dimensional space, substantially reduce active ions to surface defect energy
Amount transmitting distance, increases with temperature, and this energy transmission is obviously suppressed with process, and secondly the introducing of defect state is conducive to height
Temperature release electronic processes, further promote system bears hot quenching effect.By NaGdF4@20Ca/20Yb/2Er: NaScF4Core
Shell structural nano crystalline substance is printed on common A4 paper after being dissolved in hexamethylene, can be obtained under 980nm laser excitation, and it is significant to increase green light with temperature
The phenomenon that enhancing, as shown in figure 4, by NaGdF4@20Ca/20Yb/2Er: NaGdF4Nano-crystal with core-shell structure goes out with traditional hot-quenching
Material NaErF4Under the same terms, the phenomenon that up-conversion luminescence color is changed into yellow green from red is can be obtained in nanocrystalline mixing,
As shown in Figure 5.
A kind of antifalsification label using above-mentioned there is the antifalsification label material for bearing hot quenching effect to be made.
Embodiment 2
With the antifalsification label material for bearing hot quenching effect, molecular formula NaGdF4@40Ca/20Yb/2Er: NaScF4, pass through
Following steps are prepared:
(1) 0.8 mM of gadolinium and 8 milliliters of oleic acid are added in the three-neck flask that capacity is 50 milliliters, in nitrogen atmosphere
Protection under, adjust the temperature to 155o30 minutes are kept the temperature after C；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to
150o30 minutes are kept the temperature after C, obtains clear solution B；After B solution naturally cools to room temperature, contain 3 mMs of fluorine for 8 milliliters
The methanol solution for changing ammonium and 2 mMs of sodium hydroxides is added dropwise in B solution, wait be warming up to 60oHalf an hour is kept the temperature after C；To
Temperature all after volatilization, is risen to 280 rapidly by methanol solutionoC naturally cools to room after keeping the temperature 90 minutes at this temperature
Temperature；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by NaGdF4It is nanocrystalline be stored in it is standby in 4ml hexamethylene
With.
(2) by 0.38 mM of acetic acid scandium, 0.2 mM of ytterbium acetate, 0.02 mM of acetic acid erbium, 0.4 mM of second
Sour calcium and 8 milliliters of oleic acid are added in 50 milliliters of three-neck flasks, under the protection of nitrogen atmosphere, adjust the temperature to 150oIt is protected after C
Temperature 30 minutes；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to 150o30 minutes are kept the temperature after C, obtains clarifying molten
Liquid C；After C solution naturally cools to room temperature, nanocrystal solution prepared in (1) is added in three-neck flask, is warming up to
110o40 minutes are kept the temperature after C, obtains solution D；After hexamethylene drains, contain 3 mMs of ammonium fluorides and 2 mMs of hydrogen for 8 milliliters
The methanol solution of sodium oxide molybdena is added dropwise in solution D, wait be warming up to 60oHalf an hour is kept the temperature after C；It all volatilizees to methanol solution
Later, temperature is risen to 280 rapidlyoC naturally cools to room temperature after keeping the temperature 120 minutes at this temperature；Gained is nanocrystalline
It is washed with ethyl alcohol and hexamethylene mixed liquor, finally by NaGdF4@40Ca/20Yb/2Er: NaScF4Nano-crystal with core-shell structure is placed
In 40oFinal product is dried to obtain in C baking oven.
NaGdF made from technical solution of the present invention4@40Ca/20Yb/2Er: NaScF4It is nanocrystalline, it is seen by tem analysis
It examines and shows that size is about 11nm as shown in fig. 6, product morphology is monodispersed unifonn spherical.As shown in fig. 7, alternating temperature fluorescence light
Spectrum point, structure show and as temperature from 293K is increased to 413K, NaGdF4@40Ca/20Yb/2Er: NaScF4Core-shell structure is received
The Up-conversion Intensity of meter Jing enhances about 5.9 times.It is substantially similar to Example 1 with result.
Comparative example
Antifalsification label material, molecular formula 20Yb/2Er:NaGdF4, it is prepared by following steps: by 0.78 mM of second
Sour gadolinium, 0.2 mM of ytterbium acetate, 0.02 mM of acetic acid erbium and 8 milliliters of OA oleic acid are added in 50 milliliters of three-neck flasks,
Under the protection of nitrogen atmosphere, 155 are adjusted the temperature too30 minutes are kept the temperature after C；12 milliliters of ODE octadecylenes are added into three-neck flask,
Adjust the temperature to 150o30 minutes are kept the temperature after C, obtains clear solution A；After solution A naturally cools to room temperature, 8 milliliters are contained
3 mMs of NH4The methanol solution of F ammonium fluoride and 2 mMs of NaOH sodium hydroxides is added dropwise in solution A, wait be warming up to
60oHalf an hour is kept the temperature after C；After methanol solution all volatilization, temperature is risen to 280 rapidlyoC keeps the temperature 90 points at this temperature
Zhong Hou naturally cools to room temperature；It is washed with ethyl alcohol and hexamethylene mixed liquor by gained is nanocrystalline, finally by 20Yb/2Er:
NaGdF4It is nanocrystalline to be placed in 40oThe drying of C baking oven.
20Yb/2Er:NaGdF obtained4It is nanocrystalline, show that product morphology is monodispersed equal by tem analysis observation
Even spherical, size is about 11nm, as shown in Figure 8.As shown in figure 9, alternating temperature spectrofluorimetry structure show and with temperature from
293K is increased to 413K, 20Yb/2Er:NaGdF4Nanocrystalline Up-conversion Intensity only enhances about 2.2 times.
The advantages of this patent core-shell structure is: a, sensitized ions and active ions are limited in the shell of two-dimensional space,
Substantially reduce active ions to surface defect energy transfer distance so that the luminous intensity of system substantially weakens at room temperature；
B, hot quenching effect is born as caused by surface defect as temperature increases, in shell to dramatically increase；C, as temperature increases, by low
The defect that valence state ion doping introduces captures electronics in room temperature, and the process of high temperature release electronics further promotes negative hot-quenching and goes out effect
It answers；D, increase to 413K, 20Yb/2Er:NaGdF from 293K with temperature4Up-conversion Intensity only increase by 2.2 times,
And NaGdF4@40Ca/20Yb/2Er: NaScF4The Up-conversion Intensity of nano-crystal with core-shell structure then enhances 10.9 times.It is based on
This, can realize the multicolor luminous of temperature dependency abundant in conjunction with positive and negative hot quenching effect, and it is anti-to be conducive to be greatly promoted optics
The development of pseudo label material.
Claims (4)
1. having the antifalsification label material for bearing hot quenching effect, it is characterised in that molecular formula is a kind of antifalsification label material, molecule
Formula is NaGdF4@xCa/yYb/zEr: NaScF4, x is between 10-40, in xCa/yYb/zEr:NaScF4In correspond to Ca2+'s
Doped ions concentration is 10%-40%, and y is between 10-30, in xCa/yYb/zEr:NaScF4In correspond to Yb3+Doped ions
Concentration is 10-30%, and z is between 2-10, in xCa/yYb/zEr:NaScF4In correspond to Er3+Doped ions concentration be 2-
10%。
2. according to claim 1 have the antifalsification label material for bearing hot quenching effect, it is characterised in that by constructing core
Sensitized ions and active ions are limited in the shell of two-dimensional space by shell structure, and introduce sky by lower valency ion doping
Bit-type defect state energy capture center, hot quenching effect, i.e. luminous intensity are born in enhancing under conditions of not changing nanocrystalline size
Greatly enhance with the raising of temperature.
3. having the preparation method for the antifalsification label material for bearing hot quenching effect as described in claim 1, it is characterised in that pass through
Following steps are prepared:
0.8 mM of gadolinium and 8 milliliters of oleic acid are added in the three-neck flask that capacity is 50 milliliters, in the guarantor of nitrogen atmosphere
Under shield, 155 are adjusted the temperature too30 minutes are kept the temperature after C；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to 150oC
30 minutes are kept the temperature afterwards, obtains clear solution B；After B solution naturally cools to room temperature, by 8 milliliters containing 3 mMs of ammonium fluorides and
The methanol solution of 2 mMs of sodium hydroxides is added dropwise in B solution, wait be warming up to 60oHalf an hour is kept the temperature after C；It is molten to methanol
Temperature all after volatilization, is risen to 280 by liquidoC naturally cools to room temperature after keeping the temperature 90 minutes at this temperature；Gained is received
Meter Jing Yong ethyl alcohol and the washing of hexamethylene mixed liquor, finally by NaGdF4It is nanocrystalline be stored in it is spare in 4ml hexamethylene；
By 0.38-0.78 mMs of acetic acid scandium, 0.1-0.3 mMs of ytterbium acetate, 0.02-0.1 mMs of acetic acid erbium, 0.1-
0.4 mM of calcium acetate and 8 milliliters of oleic acid are added in 50 milliliters of three-neck flasks, under the protection of nitrogen atmosphere, by temperature tune
To 150o30 minutes are kept the temperature after C；12 milliliters of octadecylenes are added into three-neck flask, adjust the temperature to 150o30 minutes are kept the temperature after C,
Obtain clear solution C；After C solution naturally cools to room temperature, nanocrystal solution prepared in (1) is added to three-neck flask
In, it is warming up to 110o40 minutes are kept the temperature after C, obtains solution D；After hexamethylene drains, contain 3 mMs of ammonium fluorides and 2 for 8 milliliters
The methanol solution of mM sodium hydroxide is added dropwise in solution D, wait be warming up to 60oHalf an hour is kept the temperature after C；To methanol solution
All after volatilization, temperature is risen to 280oC naturally cools to room temperature after keeping the temperature 120 minutes at this temperature；Gained is received
Meter Jing Yong ethyl alcohol and the washing of hexamethylene mixed liquor, finally by NaGdF4@Ca/Yb/Er: NaScF4Nano-crystal with core-shell structure is placed in
40oFinal product is dried to obtain in C baking oven.
4. a kind of antifalsification label, it is characterised in that there is the antifalsification label material for bearing hot quenching effect using described in claim 1
Material.
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