CN109233805B - Anti-counterfeiting label material with negative thermal quenching effect and preparation method and application thereof - Google Patents
Anti-counterfeiting label material with negative thermal quenching effect and preparation method and application thereof Download PDFInfo
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- CN109233805B CN109233805B CN201811065842.XA CN201811065842A CN109233805B CN 109233805 B CN109233805 B CN 109233805B CN 201811065842 A CN201811065842 A CN 201811065842A CN 109233805 B CN109233805 B CN 109233805B
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 230000000171 quenching effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000002159 nanocrystal Substances 0.000 claims abstract description 35
- 150000002500 ions Chemical class 0.000 claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000011258 core-shell material Substances 0.000 claims description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 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 claims description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 claims description 5
- 238000010438 heat treatment Methods 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
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- LYQGMALGKYWNIU-UHFFFAOYSA-K gadolinium(3+);triacetate Chemical compound [Gd+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LYQGMALGKYWNIU-UHFFFAOYSA-K 0.000 claims description 4
- DBTMQFKUVICLQN-UHFFFAOYSA-K scandium(3+);triacetate Chemical compound [Sc+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBTMQFKUVICLQN-UHFFFAOYSA-K 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 description 11
- 238000004020 luminiscence type Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910021266 NaErF4 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WGRULTCAYDOGQK-UHFFFAOYSA-M sodium;sodium;hydroxide Chemical compound [OH-].[Na].[Na+] WGRULTCAYDOGQK-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 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
-
- 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
Abstract
The invention belongs to the field of inorganic luminescent materials. Anti-counterfeiting label material with negative thermal quenching effect, and molecular formula of anti-counterfeiting label material is NaGdF4@xCa/yYb/zEr:NaScF4X is between 10 and 40 and is xCa/yYb/zEr NaScF4Corresponds to Ca2+The concentration of the doped ions is 10-40%, y is between 10 and 30, and is xCa/yYb/zEr: NaScF4Middle corresponds to Yb3+The concentration of the doped ions is 10-30%, z is 2-10, xCa/yYb/zEr NaScF4Middle corresponds to Er3+The concentration of the doped ions is 2-10%. The material can greatly enhance the negative thermal quenching effect under the condition of not changing the size of the nanocrystal, namely, the luminous intensity is greatly enhanced along with the increase of the temperature.
Description
Technical Field
The invention belongs to the field of inorganic luminescent materials, and relates to an anti-counterfeit label material.
Technical Field
The number of phonons of the traditional thermal quenching material is gradually increased along with the increase of the temperature, the probability of nonradiative relaxation caused by phonon assistance is increased, and the fluorescence intensity of the activated ions is gradually reduced along with the increase of the temperature. The result seriously hinders the development of the lanthanide doped luminescent material in related application fields, such as large error of an optical thermometer at high temperature; the range of variation of the temperature-dependent colorimetric material with respect to the spectrum becomes limited, etc. Recent research results show that the nano material can generate a negative thermal quenching effect caused by surface defects, but the effect of the increase of the luminous intensity with the increase of the temperature is not obvious enough.
Disclosure of Invention
The invention aims to disclose an anti-counterfeiting label material which can greatly enhance the negative thermal quenching effect under the condition of not changing the size of a nano crystal, and a preparation method and application thereof.
The technical scheme of the invention is as follows: anti-counterfeiting label material with negative thermal quenching effect, and molecular formula of anti-counterfeiting label material is NaGdF4@xCa/yYb/zEr: NaScF4X is between 10 and 40 and is xCa/yYb/zEr NaScF4Corresponds to Ca2+The concentration of the doped ions is 10-40%, y is between 10 and 30, and is xCa/yYb/zEr: NaScF4Middle corresponds to Yb3+The concentration of the doped ions is 10-30%, z is between 2 and 10, and is xCa/yYb/zEr: NaScF4Middle corresponds to Er3+The concentration of the doped ions is 2-10%. Ca in the shell2+、Yb3+、Er3+And Sc3+Sc is 100% of the elements in the matrix, its concentration being in accordance with Ca2+、Yb3+、Er3+The doping ratio is adjusted accordingly.
Preferably, a core-shell structure is constructed, sensitized ions and activated ions are limited in a shell layer of a two-dimensional space, a vacancy type defect state energy trapping center is introduced through low-valence ion doping, and the negative thermal quenching effect is enhanced under the condition that the size of a nanocrystal is not changed, namely the luminous intensity is greatly enhanced along with the increase of temperature.
The preparation method of the anti-counterfeiting label material with the negative thermal quenching effect comprises the following steps:
(1) 0.8 mmol of gadolinium acetate and 8 ml of oleic acid are added into a three-neck flask with the capacity of 50 ml, and the temperature is adjusted to 155 ℃ under the protection of nitrogen atmosphereoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution B; after the solution B was naturally cooled to room temperature, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide was added dropwise to the solution B, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution is completely volatilized, the temperature is quickly raised to 280 DEGoC, preserving the heat at the temperature for 90 minutes, and naturally cooling to room temperature; washing the obtained nanocrystal with mixed solution of ethanol and cyclohexane, and washing with waterAdding NaGdF4Storing the nano-crystals in 4ml of cyclohexane for later use;
(2) 0.38 to 0.78 millimole of scandium acetate, 0.1 to 0.3 millimole of ytterbium acetate, 0.02 to 0.1 millimole of erbium acetate, 0.1 to 0.4 millimole of calcium acetate and 8 ml of oleic acid are added into a 50 ml three-neck flask, and the temperature is adjusted to 150 ℃ under the protection of nitrogen atmosphereoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution C; after the solution C is naturally cooled to room temperature, adding the nanocrystalline solution prepared in the step (1) into a three-neck flask, and heating to 110 DEGoC, preserving the heat for 40 minutes to obtain a solution D; after the cyclohexane had drained, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide were added dropwise to the solution D, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution is completely volatilized, the temperature is quickly raised to 280 DEGoC, preserving the heat at the temperature for 120 minutes, and naturally cooling to room temperature; washing the obtained nanocrystal with mixed solution of ethanol and cyclohexane, and finally washing the NaGdF4@Ca/Yb/Er: NaScF4The core-shell structure nanocrystal is placed in a position of 40oAnd C, drying in an oven to obtain a final product.
An anti-counterfeiting label uses the anti-counterfeiting label material with the negative thermal quenching effect.
The invention has the beneficial effects that: construction of NaGdF4@xCa/yYb/zEr: NaScF4The core-shell structure limits sensitized ions and activated ions in a shell layer of a two-dimensional space, and further introduces vacancy type defect state energy capture centers through low valence state ion doping. The core-shell structure has the advantages that: a. the sensitized ions and the activated ions are limited in a shell layer of a two-dimensional space, so that the energy transfer distance from the activated ions to surface defects is greatly shortened, and the luminous intensity of a system at room temperature is greatly reduced; b. with the temperature rise, the negative thermal quenching effect caused by the surface defects in the shell layer is obviously increased; c. defects introduced by low valence ion doping as the temperature increases areElectrons are captured at room temperature, and the negative thermal quenching effect is further promoted in the process of releasing the electrons at high temperature; based on this, the combination of positive and negative thermal quenching effects can realize rich temperature-dependent multicolor luminescence, which is beneficial to greatly promoting the development of optical anti-counterfeiting label materials.
Drawings
FIG. 1: NaGdF in example 14@20Ca/20Yb/2Er: NaScF4XRD pattern of core-shell structure nanocrystal;
FIG. 2: NaGdF in example 14@20Ca/20Yb/2Er: NaScF4TEM image (a) of core-shell structure nanocrystals, high angle annular dark field image (b) and distribution patterns of Na (c), Gd (d), F (e), Yb (f) and Ca (g) elements;
FIG. 3: NaGdF in example 14@20Ca/20Yb/2Er: NaScF4A variable-temperature fluorescence spectrogram (a) and an amplitude enhancement trend chart (b) of core-shell structure nanocrystals under the excitation of 980nm wavelength;
FIG. 4: NaGdF in example 14@20Ca/20Yb/2Er: NaScF4The pattern prepared by the core-shell structure nanocrystalline is a graph of the change of the luminous intensity with the temperature under the excitation of 980nm wavelength and under the conditions of 293K (a) and 413K (b);
FIG. 5: NaGdF in example 14@20Ca/20Yb/2Er: NaGdF4Core-shell structure nanocrystalline and 20Yb/1Tm: NaGdF4The patterns prepared by mixing the nanocrystals are in a graph of the change of the luminous color and the intensity along with the temperature under the excitation of 980nm and under the temperature conditions of 293K (a) and 413K (b);
FIG. 6: NaGdF in example 24@40Ca/20Yb/2Er: NaScF4TEM image of core-shell structure nanocrystal, and inset is the corresponding particle size distribution diagram;
FIG. 7: NaGdF in example 24@40Ca/20Yb/2Er: NaScF4A variable-temperature fluorescence spectrogram (a) and an amplitude enhancement trend chart (b) of core-shell structure nanocrystals under the excitation of 980nm wavelength;
FIG. 8: comparative example 20Yb/2Er NaGdF4A TEM image of the nanocrystal;
FIG. 9: comparative example 20Yb/2Er NaGdF4NanocrystalAnd (b) a variable temperature fluorescence spectrum graph (a) and an amplitude enhancement trend graph (b) thereof under the excitation of the wavelength of 980 nm.
Detailed Description
The invention is further described with reference to the drawings and examples in the following description.
Example 1
Anti-counterfeiting label material with negative thermal quenching effect, and molecular formula of anti-counterfeiting label material is NaGdF4@20Ca/20Yb/2Er: NaScF4The preparation method comprises the following steps:
(1) 0.8 mmol of gadolinium acetate and 8 ml of oleic acid are added into a three-neck flask with the capacity of 50 ml, and the temperature is adjusted to 155 ℃ under the protection of nitrogen atmosphereoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution B; after the solution B was naturally cooled to room temperature, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide was added dropwise to the solution B, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution is completely volatilized, the temperature is quickly raised to 280 DEGoC, preserving the heat at the temperature for 90 minutes, and naturally cooling to room temperature; washing the obtained nano crystal with mixed solution of ethanol and cyclohexane, and finally washing the NaGdF4Storing the nano-crystals in 4ml of cyclohexane for later use;
(2) 0.58 mmol of scandium acetate, 0.2 mmol of ytterbium acetate, 0.02 mmol of erbium acetate, 0.2 mmol of calcium acetate and 8 ml of oleic acid are placed in a 50 ml three-neck flask, and the temperature is adjusted to 150 ℃ under the protection of nitrogenoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution C; after the solution C is naturally cooled to room temperature, adding the nanocrystalline solution prepared in the step (1) into a three-neck flask, and heating to 110 DEGoC, preserving the heat for 40 minutes to obtain a solution D; after the cyclohexane had drained, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide were added dropwise to the solution D, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution is completely volatilized, the temperature is quickly raised to 280 DEGoC, preserving the heat at the temperature for 120 minutes, and naturally cooling to room temperature; washing the obtained nanocrystal with mixed solution of ethanol and cyclohexane, and finally washing the NaGdF4@20Ca/20Yb/2Er: NaScF4The core-shell structure nanocrystal is placed in a position of 40oAnd C, drying in an oven to obtain a final product.
NaGdF prepared by the technical scheme of the invention4@20Ca/20Yb/2Er: NaScF4Nanocrystalline, as shown in fig. 1, by XRD analysis, the obtained product was all pure hexagonal phase; as shown in FIG. 2, TEM and EDS-mapping analysis showed that the product morphology is monodisperse uniform spheres with a size of about 11nm, and the doped sensitizing ions and activating ions are confined in a two-dimensional shell. As shown in FIG. 3, the temperature-variable fluorescence spectroscopy shows that NaGdF increases with temperature from 293K to 413K4@20Ca/20Yb/2Er: NaScF4The up-conversion luminescence intensity of the core-shell structure nanocrystal is enhanced by about 10.9 times. The sensitized ions and the activated ions are limited in the shell layer of the two-dimensional space, so that the energy transfer distance from the activated ions to the surface defects is greatly shortened, the energy transfer is obviously inhibited along with the process along with the rise of the temperature, and the introduction of the defect state is favorable for the process of releasing electrons at high temperature, thereby further promoting the negative thermal quenching effect of the system. Adding NaGdF4@20Ca/20Yb/2Er: NaScF4The core-shell structure nanocrystal is dissolved in cyclohexane and printed on common A4 paper, and the phenomenon that green light is obviously enhanced along with temperature rise under the excitation of 980nm laser can be obtained, as shown in figure 4, NaGdF is added4@20Ca/20Yb/2Er: NaGdF4Core-shell structure nanocrystalline and traditional thermal quenching material NaErF4The phenomenon that the up-conversion luminescent color is changed from red to yellow green can be obtained by mixing the nanocrystals under the same conditions, as shown in fig. 5.
An anti-counterfeit label is made of the anti-counterfeit label material with the negative thermal quenching effect.
Example 2
Anti-counterfeiting label material with negative thermal quenching effect, and molecular formula of anti-counterfeiting label material is NaGdF4@40Ca/20Yb/2Er: NaScF4The preparation method comprises the following steps:
(1) 0.8 millimole of gadolinium acetateAdding 8 ml of oleic acid into a three-neck flask with the capacity of 50 ml, and adjusting the temperature to 155 ℃ under the protection of nitrogen atmosphereoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution B; after the solution B was naturally cooled to room temperature, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide was added dropwise to the solution B, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution is completely volatilized, the temperature is quickly raised to 280 DEGoC, preserving the heat at the temperature for 90 minutes, and naturally cooling to room temperature; washing the obtained nano crystal with mixed solution of ethanol and cyclohexane, and finally washing the NaGdF4The nanocrystals were stored in 4ml of cyclohexane for later use.
(2) 0.38 mmol of scandium acetate, 0.2 mmol of ytterbium acetate, 0.02 mmol of erbium acetate, 0.4 mmol of calcium acetate and 8 ml of oleic acid are placed in a 50 ml three-neck flask, and the temperature is adjusted to 150 ℃ under nitrogen protectionoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution C; after the solution C is naturally cooled to room temperature, adding the nanocrystalline solution prepared in the step (1) into a three-neck flask, and heating to 110 DEGoC, preserving the heat for 40 minutes to obtain a solution D; after the cyclohexane had drained, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide were added dropwise to the solution D, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution is completely volatilized, the temperature is quickly raised to 280 DEGoC, preserving the heat at the temperature for 120 minutes, and naturally cooling to room temperature; washing the obtained nanocrystal with mixed solution of ethanol and cyclohexane, and finally washing the NaGdF4@40Ca/20Yb/2Er: NaScF4The core-shell structure nanocrystal is placed in a position of 40oAnd C, drying in an oven to obtain a final product.
NaGdF prepared by the technical scheme of the invention4@40Ca/20Yb/2Er: NaScF4The nano-crystalline, observed by TEM analysis, shows that the morphology of the product is monodisperse uniform spheres with a size of about 11nm, as shown in fig. 6. FIG. 7 shows a structure chart of temperature-variable fluorescence spectraWhile NaGdF increases with temperature from 293K to 413K4@40Ca/20Yb/2Er: NaScF4The up-conversion luminescence intensity of the core-shell structure nanocrystal is enhanced by about 5.9 times. The results are essentially similar to example 1.
Comparative example
The anti-counterfeit label material has a molecular formula of 20Yb/2Er and NaGdF4The preparation method comprises the following steps: 0.78 mmol of gadolinium acetate, 0.2 mmol of ytterbium acetate, 0.02 mmol of erbium acetate and 8 ml of OA oleic acid are placed in a 50 ml three-neck flask, and the temperature is adjusted to 155 ℃ under the protection of nitrogen atmosphereoC, preserving the heat for 30 minutes; 12 ml of ODE octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution A; after the solution A had cooled to room temperature, 8 ml of the solution containing 3 mmol of NH4F, adding a methanol solution of ammonium fluoride and 2 millimoles of NaOH sodium hydroxide into the solution A dropwise, and heating to 60 DEGoKeeping the temperature for half an hour after C; after the methanol solution is completely volatilized, the temperature is quickly raised to 280 DEGoC, preserving the heat at the temperature for 90 minutes, and naturally cooling to room temperature; washing the obtained nano-crystal with mixed solution of ethanol and cyclohexane, and finally washing the nano-crystal with 20Yb/2Er and NaGdF4The nanocrystal is arranged in a 40oAnd C, drying in an oven.
The prepared 20Yb/2Er is NaGdF4The appearance of the product is monodisperse uniform spherical with the size of about 11nm as shown in figure 8. As shown in FIG. 9, the temperature-variable fluorescence spectroscopy structure shows that 20Yb/2Er: NaGdF increases with temperature from 293K to 413K4The up-conversion luminescence intensity of the nanocrystals increased only about 2.2 times.
The advantage of this patent nucleocapsid structure is: a. the sensitized ions and the activated ions are limited in a shell layer of a two-dimensional space, so that the energy transfer distance from the activated ions to surface defects is greatly shortened, and the luminous intensity of a system at room temperature is greatly reduced; b. with the temperature rise, the negative thermal quenching effect caused by the surface defects in the shell layer is obviously increased; c. with the temperature rise, the defects introduced by the low-valence ion doping capture electrons at room temperature, and the process of releasing the electrons at high temperature further promotes the negative thermal quenching effect; d.with the temperature increased from 293K to 413K, 20Yb/2Er: NaGdF4The up-conversion luminescence intensity of (1) is increased by only 2.2 times, while NaGdF4@40Ca/20Yb/2Er: NaScF4The up-conversion luminescence intensity of the core-shell structure nanocrystal is enhanced by 10.9 times. Based on this, the combination of positive and negative thermal quenching effects can realize rich temperature-dependent multicolor luminescence, which is beneficial to greatly promoting the development of optical anti-counterfeiting label materials.
Claims (3)
1. The anti-counterfeiting label material with negative thermal quenching effect is characterized in that the molecular formula is NaGdF4@xCa/yYb/zEr: NaScF4X is between 10 and 40 and is xCa/yYb/zEr NaScF4Corresponds to Ca2+The concentration of the doped ions is 10-40%, y is between 10 and 30, and is xCa/yYb/zEr: NaScF4Middle corresponds to Yb3+The concentration of the doped ions is 10-30%, z is between 2 and 10, and is xCa/yYb/zEr: NaScF4Middle corresponds to Er3+The concentration of the doped ions is 2-10%.
2. The preparation method of the anti-counterfeiting label material with the negative thermal quenching effect according to claim 1, which is characterized by comprising the following steps:
(1) 0.8 mmol of gadolinium acetate and 8 ml of oleic acid are added into a three-neck flask with the capacity of 50 ml, and the temperature is adjusted to 155 ℃ under the protection of nitrogen atmosphereoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution B; after the solution B was naturally cooled to room temperature, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide was added dropwise to the solution B, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution was completely volatilized, the temperature was raised to 280 deg.CoC, preserving the heat at the temperature for 90 minutes, and naturally cooling to room temperature; washing the obtained nano crystal with mixed solution of ethanol and cyclohexane, and finally washing the NaGdF4Storing the nano-crystals in 4ml of cyclohexane for later use;
(2) 0.38 to 0.78 millimole of scandium acetate, 0.1 to 0.3 millimole of ytterbium acetate, 0.02 to 0.1 millimole of erbium acetate and 0.1 to 0.4 millimole of erbium acetateAdding molal calcium acetate and 8 ml oleic acid into a 50 ml three-neck flask, and adjusting the temperature to 150 ℃ under the protection of nitrogen atmosphereoC, preserving the heat for 30 minutes; 12 ml of octadecene were added to a three-necked flask and the temperature was adjusted to 150 deg.CoC, preserving the heat for 30 minutes to obtain a clear solution C; after the solution C is naturally cooled to room temperature, adding the nanocrystalline solution prepared in the step (1) into a three-neck flask, and heating to 110 DEGoC, preserving the heat for 40 minutes to obtain a solution D; after the cyclohexane had drained, 8 ml of a methanol solution containing 3 mmol of ammonium fluoride and 2 mmol of sodium hydroxide were added dropwise to solution D, and the temperature was raised to 60%oKeeping the temperature for half an hour after C; after the methanol solution was completely volatilized, the temperature was raised to 280 deg.CoC, preserving the heat at the temperature for 120 minutes, and naturally cooling to room temperature; washing the obtained nanocrystal with mixed solution of ethanol and cyclohexane, and finally washing the NaGdF4@Ca/Yb/Er: NaScF4The core-shell structure nanocrystal is placed in a position of 40oAnd C, drying in an oven to obtain a final product.
3. A security label characterized by using the security label material having a negative thermal quenching effect according to claim 1.
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