CN115948165A - UCNPs/CsPbX 3 Composite material, preparation method and application - Google Patents
UCNPs/CsPbX 3 Composite material, preparation method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to UCNPs/CsPbX 3 Composite material, preparation method and application, wherein the main component of the composite material is cubic perovskite CsPbX 3 Nanocrystalline and hexagonal phase core-shell NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 Upconversion nanoparticles (UCNPs), both linked by long chain organic ligands. UCNPs/CsPbX compared to the non-radiative form of Dexter short-range energy transfer 3 The energy transfer of the composite material system follows a photon reabsorption mechanism, and CsPbX is used for sensitizing UCNPs 3 The ultra-high up-conversion luminous efficiency can be shown, the characteristic of tunable luminescence is achieved, and the problem of coupling limitation of energy transfer on molecules is solved. The fluorescent ink is packaged by photosensitive resin, so that the fluorescent ink has environmental resistance, and can be applied to the field of advanced anti-counterfeiting materials.
Description
Technical Field
The invention relates to UCNPs/CsPbX 3 Composite material, preparation method and application, belonging to the technical field of luminescent material.
Background
Counterfeiting is a global, long-standing problem that has significant negative impact on socioeconomic and poses a security threat to individuals, companies, and the entire society. Traditional anti-counterfeit labels, such as watermarks or holographic patterns, have limited encoding capacity and are easy to copy, so that corresponding protective products are easy to counterfeit. Compared with the prior art, the chemical anti-counterfeiting method has the advantages of high selectivity and complexity, short reading time, easiness in chemical detection and the like, and meanwhile has enough diversity, so that the technical requirement for counterfeiting is high, and the counterfeiting probability can be effectively reduced.
Up-conversion nanoparticles (UCNPs) are used as materials which are applied to the anti-counterfeiting field at first, and are widely applied to anti-counterfeiting marks of currency and files. In practical applications, the most common upconversion material is a Yb and Tm (Er) co-doped nanocrystal, however, this type of upconversion anti-counterfeiting material can only show almost invariable color under excitation, and therefore, the anti-counterfeiting pattern constructed by the upconversion anti-counterfeiting material is likely to be imitated by other substitutes with similar emission.
All-inorganic perovskite CsPbX 3 The quantum dots have excellent physicochemical properties such as large absorption coefficient, high photoluminescence quantum yield, and multiband emission by changing the halide component. These unique properties make it potentially usefulAn optical anti-counterfeiting material with application value. However, the perovskite CsPbX 3 Quantum dots are very sensitive to temperature, humidity and ultraviolet light, which limits their long-term deployment in large-scale commercialization. Furthermore, although CsPbX 3 The quantum dots have larger absorption cross section in a blue-violet light area, but the absorption capacity to near infrared light is insufficient, and the main reason is CsPbX 3 Quantum dots lack intermediate energy levels for energy transfer. In order to realize the two-photon up-conversion of perovskite, the laser needs to have higher energy density, but the price of the near-infrared pulse laser is often higher, so that the full inorganic perovskite CsPbX is limited 3 Application of quantum dots in anti-counterfeiting materials. There are patents by combining all-inorganic perovskites CsPbX 3 The CsPbX is improved by combining with an up-conversion luminescent material in a physical mixing mode 3 The quantum dot has the defect of insufficient absorption capacity of near infrared light, but the physical combination mode has limited influence on the crystal phase structure of the product, so that the CsPbX is finally influenced 3 The improvement of the energy transfer efficiency is not obvious, and the effect of improving the absorption capability of near infrared light is not ideal.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a UCNPs/CsPbX 3 The composite material has the characteristics of fluorescence up-conversion, high energy transfer efficiency and the like, and can be used as fluorescent ink for writing to realize multi-mode fluorescence anti-counterfeiting by packaging UVCR and giving consideration to certain environmental resistance.
The technical scheme for solving the technical problems is as follows:
one purpose of the invention is to provide UCNPs/CsPbX 3 The UCNPs are nanometer materials doped with Yb and Tm and having a core-shell structure, and the CsPbX is 3 Wherein X is Br and/or I, wherein Br: the ratio of I is 1.
On the basis of the technical scheme, the invention can also make the following improvements:
further, the UCNPs have a structural formula of NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 。
Furthermore, in the crystal phase structure, UCNPs crystals are in a spherical core-shell hexagonal phase, csPbX 3 The crystal is cubic, and the CsPbX is 3 The crystal is close to the UCNPs crystal, and CsPbX is close to the UCNPs crystal 3 CsPbX with crystal size smaller than that far away from the UCNPs crystal 3 Crystal size.
Further, the preparation of the UCNPs comprises the following raw materials: y (CH) 3 CO 2 ) 3 ·H 2 O、Yb(CH 3 CO 2 ) 3 ·4H 2 O、Tm(CH 3 CO 2 ) 3 ·H 2 O, oleic acid, octadecene, NH-containing 4 F and NaOH in methanol.
Further, the CsPbX 3 The preparation method comprises the following steps: cs 2 CO 3 Octadecene, oleic acid, oleylamine and PbX 2 Wherein X is Br and/or I.
The second purpose of the invention is to provide a UCNPs/CsPbX as mentioned above 3 The preparation method of the composite material adopts a high-temperature coprecipitation method and a thermal injection method for synthesis, firstly adopts the high-temperature coprecipitation method to prepare the nuclear shell UCNPs nano particles, and secondly thermally injects the nuclear shell UCNPs nano particles into CsPbX 3 During the synthesis of the nanocrystals. In the nucleation process of the perovskite quantum dots, a part of the nuclear dots are attached to the surface of UCNPs through organic long-chain ligands, so that the local growth competition of the nuclear dots is caused, and because of the uneven competitive growth, the generated small-size perovskite quantum dots are close to the UCNPs, so that the energy transfer efficiency is improved.
Further, the preparation method specifically comprises the following steps:
(1) Nuclear NaYF 4 :Yb 3+ ，Tm 3+ The preparation of (1):
mixing raw material Y (CH) 3 CO 2 ) 3 ·H 2 O、Yb(CH 3 CO 2 ) 3 ·4H 2 O、Tm(CH 3 CO 2 ) 3 ·H 2 Placing O, oleic acid and octadecylene in a flask, exhausting air and water, and dissolving solid powder(ii) a Adding a solution containing NH 4 F and NaOH methanol solution, the temperature is set to be 45-55 ℃, the reaction is carried out under the circulation of protective atmosphere, the methanol and the water are removed, the temperature is raised to 250-350 ℃ for continuous reaction, after the reaction is finished, the heating is stopped, and the solution is cooled to the room temperature; adding ethanol into the solution, centrifuging to obtain a precipitate, repeatedly cleaning the precipitate, and finally dissolving the precipitate in cyclohexane;
(2) Core-shell NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 Preparation of (UCNPs):
mixing raw material Y (CH) 3 CO 2 ) 3 ·H 2 Placing O, oleic acid and octadecylene in a flask, exhausting air and moisture, and dissolving solid powder; adding the NaYF prepared in the step (1) into the solution 4 :Yb 3+ ，Tm 3+ After stirring evenly, continuously adding the solution containing NH 4 F and NaOH methanol solution, the temperature is set to be 45-55 ℃, the reaction is carried out under the circulation of protective atmosphere, methanol and water are removed, the temperature is raised to 250-350 ℃, the reaction is continued, after the reaction is finished, the heating is stopped, and the solution is cooled to the room temperature; adding ethanol and cyclohexane into the solution, centrifuging to obtain a precipitate, repeatedly cleaning the precipitate, and finally dissolving the precipitate in toluene;
(3)UCNPs/CsPbX 3 preparing a composite material:
(1) preparation of a precursor: mixing Cs 2 CO 3 Octadecylene and oleic acid are put in a container until the C is 2 CO 3 Completely dissolving to obtain a cesium salt precursor solution;
(2) mixing PbX 2 Placing with octadecene in a container, injecting oleic acid and oleylamine under protective atmosphere, and dissolving PbX 2 After the dissolution is finished, injecting the NaYF obtained in the step (2) 4 :Yb 3+ ,Tm 3+ @NaYF 4 Toluene solution, heating the solution to 150-180 deg.C, injecting cesium salt precursor solution obtained in the step (1), centrifuging the obtained product, and removing the supernatant to obtain UCNPs/CsPbBr 3 A composite material.
Further, the protective atmosphere is nitrogen.
Object of the inventionIt is to provide a UCNPs/CsPbX as described above 3 The application of the composite material in preparing anti-counterfeiting materials. By encapsulating photosensitive resin in UCNPs/CsPbX 3 The anti-counterfeiting material is prepared.
The invention has the advantages that: the invention aims to prepare up-conversion UCNPs/CsPbX applicable to up-conversion luminescent devices and multi-mode anti-counterfeiting 3 The composite material has high up-conversion energy transfer efficiency through an ERA mechanism, can realize the absorption of short-wave near infrared light and emits high-energy photons with the wavelength within 500nm-700 nm. For the field of up-conversion luminescence, the composite material system designed by the invention has wide application prospect. The composite material prepared by the invention takes UCNPs as physical energy transfer energy level, and releases high-energy photons after absorbing 980nm exciting light (C:) 1 D 2 - 3 F 4 ， 1 G 4 - 3 H 6 ) High-energy photons are utilized by the perovskite quantum dots to release characteristic fluorescence of the perovskite quantum dots with edge exciton radiation recombination again, and compared with the traditional up-conversion luminescent material, the UCNPs/CsPbX luminescent material has the advantages that 3 The composite material has the characteristic of tunable emission wavelength, and the luminescent color can be switched at will according to the proportion of perovskite quantum dot halogen ions. The composite material has good stability after being packaged by the photosensitive polymer, and is more beneficial to the application in the fields of up-conversion luminescent devices and multi-mode anti-counterfeiting.
Drawings
FIG. 1 shows the UCNPs/CsPbX of the present invention 3 The energy transfer mechanism of the composite;
FIG. 2 shows UCNPs/CsPbBr in example 1 3 TEM images of the composite material;
FIG. 3 shows UCNPs/CsPbBr in example 1 3 Spectral images of the composite material under laser excitation;
FIG. 4 shows UCNPs/CsPbX in examples 1-6 3 The composite material is excited by 980nm laser to change images along with the spectrum of different halogen proportions;
FIG. 5 shows UCNPs/CsPbBr in example 1 3 Time-resolved fluorescence attenuation light of composite material under excitation of 980nm pulse laserA spectrum;
FIG. 6 shows UCNPs/CsPbBr in example 1 3 And UCNPs/CsPbBr 3 The fluorescence intensity attenuation spectrum of the @ UVCR composite film after a dripping experiment;
FIG. 7 shows UCNPs/CsPbBr in example 1 3 The @ UVCR composite material dual-mode anti-counterfeiting diagram.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
1. UCNPs/CsPbX 3 The composite material is synthesized by a high-temperature coprecipitation method and a hot injection method, and comprises the following components in percentage by weight:
(1) Nuclear NaYF 4 :Yb 3+ ，Tm 3+ ：Y(CH 3 CO 2 ) 3 ·H 2 O 1.63g,Yb(CH 3 CO 2 ) 3 ·4H 2 O 1.06g，Tm(CH 3 CO 2 ) 3 ·H 2 0.035g O, 6.5mL oleic acid, 20mL octadecene, methanol solution (containing 1.48g NH) 4 F and 1g NaOH) 10mL.
It is worth mentioning that the methanol solution needs to be prepared in advance and treated by ultrasonication to make NaOH and NH 4 F is completely dissolved, so that the influence on the size and quality of the nano particles due to the low ion content caused by insufficient dissolution or excessive NaF generation is prevented.
(2) Core-shell NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 (UCNPs)：Y(CH 3 CO 2 ) 3 ·H 2 O2.65 g, oleic acid 6.5mL, octadecene 20mL, methanol solution (containing 1.48 gNH) 4 F and 1g NaOH) 10mL.
It is worth mentioning that the methanol solution needs to be prepared in advance and treated with ultrasound to make NaOH and NH 4 F is completely dissolved, so that the influence on the thickness of the shell layer of the nanoparticle caused by low ion content due to insufficient dissolution or excessive NaF generation is prevented.
(3)CsPbX 3 (X = Br and/or I) nanocrystals: (1) before preparationBody: cs 2 CO 3 0.16g, 7mL of octadecene and 0.5mL of oleic acid. (2) Dissolving lead halide inorganic salt: pbX 3 0.188mmol (where the Br/I ratio is 1.
2. The UCNPs/CsPbX 3 The specific synthetic method of the composite material comprises the following steps:
(1) Nuclear NaYF 4 :Yb 3+ ，Tm 3+ The preparation of (1):
mixing Y (CH) 3 CO 2 ) 3 ·H 2 O 1.63g,Yb(CH 3 CO 2 ) 3 ·4H 2 O 1.06g，Tm(CH 3 CO 2 ) 3 ·H 2 0.035g of O, 6.5mL of oleic acid and 20mL of octadecene were placed in a 100mL three-necked flask. The three-neck flask is arranged on a heating jacket with a temperature control device and magnetic stirring, and the heating system also comprises a double-row pipe device which can freely switch vacuum and nitrogen. After the three-neck flask is completely arranged, nitrogen is introduced for three times, the air in the flask is exhausted, and then the temperature is heated to 120 ℃ under vacuum and kept for 30 minutes to remove the water contained in the solution. After the water removal was complete, the temperature was raised to 150 ℃ and held for 30-60 minutes to completely dissolve the solid powder. After dissolution was complete, the solution appeared clear and pale yellow. The heating was turned off and the solution was allowed to cool to room temperature.
Under the standard atmospheric pressure, the rubber plug of the three-neck flask is opened, the rotating speed of the rotor is increased, and 10mL of methanol solution (containing 1.48g of NH) is injected 4 F and 1g naoh). After the injection was complete, the temperature was set at around 50 ℃ and kept under a stream of nitrogen for 1 hour until the methanol was removed. Notably, the methanol gas should be purged into the deionized water or other solvent with the nitrogen flow to avoid hazardous gases. After the reaction was completed, the solution was slightly cloudy and milky yellow. At this point, the three-necked flask plug was re-fastened and the nitrogen was slowly purged to remove the residual methanol solution. The temperature was raised to 110 ℃ under vacuum to further remove methanol and residual moisture. The atmosphere was switched to a nitrogen atmosphere and the temperature was raised to 300 ℃ for 1 hour. After the reaction is finished, the solution is in a dark red state, the heating device is closed, and the solution is cooled to room temperature.
At room temperature, 20mL of ethanol is injected into the solution in batches, and finally the solution is placed into a centrifuge tube for centrifugation, wherein the rotation speed is 10000r/min, and the centrifugation time is 10 minutes. After the centrifugation is finished, a precipitated product is obtained, the precipitated product is repeatedly washed for 3 times by using cyclohexane and ethanol solution, and finally the precipitated product is dissolved in 10mL of cyclohexane.
(2) Core-shell NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 Preparation of (UCNPs):
mixing Y (CH) 3 CO 2 ) 3 ·H 2 O2.65 g, oleic acid 6.5mL, octadecene 20mL were placed in a 100mL three-necked flask. After the three-neck flask is completely arranged, nitrogen is introduced for three times, the air in the flask is exhausted, and then the temperature is heated to 120 ℃ under vacuum and kept for 30 minutes to remove the water contained in the solution. After the water removal was complete, the temperature was raised to 150 ℃ and held for 30-60 minutes to completely dissolve the solid powder. After dissolution was complete, the solution appeared clear and pale yellow. The heating was turned off and the solution was allowed to cool to room temperature.
Opening a rubber plug of the three-neck flask under the standard atmospheric pressure, increasing the rotation speed of a rotor, adding the UCNPs nucleus prepared in the step (1) into the solution, and then injecting 10mL of methanol solution (containing 1.48g of NH) 4 F and 1g naoh). After the injection was complete, the temperature was set at around 50 ℃ and kept under a stream of nitrogen for 1 hour until the methanol was removed. Notably, the methanol gas should be purged into the deionized water or other solvent with the nitrogen flow to avoid hazardous gases. After the reaction was completed, the solution was slightly cloudy and milky yellow. At this point, the three-necked flask plug was re-fastened and the nitrogen was slowly purged to remove the residual methanol solution. The temperature was raised to 110 ℃ under vacuum to further remove methanol and residual moisture. The atmosphere was switched to a nitrogen atmosphere and the temperature was raised to 300 ℃ for 1 hour. After the reaction is finished, the solution is in a dark red state, the heating device is closed, and the solution is cooled to room temperature. The target product was repeatedly washed with ethanol and cyclohexane by centrifugation, and then the precipitate was dissolved in 10mL of a toluene solution.
(3)UCNPs/CsPbX 3 (X = Br/I) preparation of composite material:
(1) mixing Cs 2 CO 3 0.16g, 7mL of octadecene and 0.5mL of oleic acid are placed in a 50mL three-neck flask, nitrogen is introduced for three times, and air in the three-neck flask is exhausted. The temperature was then raised to 120 ℃ under vacuum for 30 minutes to drive off the water in the solution. Finally, the temperature is raised to 160 ℃ under nitrogen until Cs is reached 2 CO 3 Dissolution is complete, resulting in a clear cesium salt precursor solution.
(2) 0.188mmol of PbBr 2 Placed in a 50mL three-necked flask with 6mL of octadecene. The solution was then heated to 120 ℃ under vacuum for 30 minutes to remove water. The reaction mixture was switched to nitrogen, and 0.5mL of oleic acid and 0.5mL of oleylamine were injected to dissolve the lead halide inorganic salt. After completion of the dissolution, 0.25mL of the core-shell UCNPs toluene solution obtained in step (2) above was injected, and then switched to vacuum to remove toluene and residual moisture. Finally, the temperature of the solution was raised to 160 ℃ under nitrogen, 0.4mL of the cesium salt precursor solution obtained in step (1) was injected, and after reacting for 10 seconds, the solution was cooled in ice water. The resulting product was centrifuged at 10000r/min for 10 minutes, the supernatant was removed, and the precipitate was dissolved in 5mL of toluene solution. After the operation of the round is finished, UCNPs/CsPbBr can be obtained 3 A composite material.
3. UCNPs/CsPbBr with up-conversion luminescence and environmental stability 3 The @ UVCR composite material is prepared in the following way:
1mL of photosensitive resin (UVCR) was mixed with 0.5mL of UCNPs/CsPbBr 3 The toluene solution was mixed and stirred for 20 seconds to form a homogeneous solution. The solution was placed in a vacuum oven set at 35 ℃ for 150 minutes to remove the toluene. The obtained product can be used as fluorescent ink and is solidified by ultraviolet light. Preferably, the photosensitive resin is epoxy resin, which includes a curing agent, a photoinitiator and a diluent, and can be polymerized under ultraviolet light.
Example 2
Unlike example 1, the lead halide PbX of this example 2 The Br/I ratio of (B) is 0.8, and the rest is the same as that in example 1 and is not repeated.
Example 3
Unlike example 1Also, the lead halide PbX of the present example 2 The Br/I ratio of (B) is 0.6, and the rest is the same as that in example 1 and is not repeated.
Example 4
Unlike example 1, the lead halide PbX of this example 2 The Br/I ratio of (B) is 0.4, 0.6, and the rest is the same as in example 1 and is not repeated.
Example 5
Unlike example 1, the lead halide PbX of this example 2 The Br/I ratio of (B)/(A) was 0.2, which was the same as in example 1 and was not repeated herein.
Example 6
Unlike example 1, the lead halide PbX of this example 2 The Br/I ratio of (B) is 0, and the rest is the same as example 1 and will not be described again.
FIG. 1 shows UCNPs/CsPbX of examples 1 to 6 of the present invention 3 (X = Br and/or I) energy transfer mechanism of the composite. In the process of energy transfer, yb 3+ Energy transfer from 980nm laser to Tm by energy transfer and excited state absorption 3+ 。Tm 3 + The inner 4f orbital electron of (a) undergoes a radiative transition to release a high-energy photon (a) 1 D 2 - 3 F 4 ， 1 G 4 - 3 H 6 ) And is re-coated with perovskite CsPbX 3 And (4) absorbing. CsPbX upon sensitization of UCNPs 3 Characteristic fluorescence in the visible band is released.
The UCNPs/CsPbX prepared by the method 3 (X = Br and/or I) composites were subjected to various performance tests, with the following results:
FIG. 2 shows UCNPs/CsPbBr in example 1 of the present invention 3 TEM images of the composite. The round material is Yb and Tm doped UCNPs, and the average size is about 35 nm. The cubic material is CsPbBr 3 The average size of the nano crystals after statistics is about 12 nm. In the experimental process, UCNPs as a matrix material participate in CsPbX 3 And (5) growing the crystal. In CsPbX 3 When the crystals are nucleated, the UCNPs provide a large number of crystal nucleus attachment sites, so that nuclear sites in the solution and nuclear sites on the surface of the UCNPs compete with each other, and the result is thatCsPbBr 3 Non-uniform growth of nanocrystals. Small size CsPbBr after reaction 3 The nanocrystals will close up on the surface of the UCNPs.
FIG. 3 (a) shows UCNPs/CsPbBr in example 1 of the present invention 3 Spectral images of the composite material under 980nm laser excitation. 450nm,476nm and 520nm light-emitting regions can be observed under the irradiation of 980nm laser, which are respectively derived from Tm ions 1 D 2 - 3 F 4 ， 1 G 4 - 3 H 6 And CsPbBr, and 3 band edge exciton transitions of nanocrystals. By increasing CsPbBr 3 The energy transfer efficiency inside the nanoparticle system can be nearly 100% by the proportion of the nanocrystals.
FIG. 3 (b) is a diagram showing UCNPs/CsPbBr in example 1 of the present invention 3 Spectral images of the composite material under 365nm laser excitation. UCNPs/CsPbBr is clearly shown in the figure 3 Besides the up-conversion luminescence characteristic, the composite material also retains the excellent photoluminescence capability under ultraviolet light.
FIG. 4 shows UCNPs/CsPbX in examples 1 to 6 of the present invention 3 The composite material is excited by 980nm laser to change images along with the spectrum change of different halogen proportions. Spectral changes in the images demonstrate the UCNPs/CsPbX of the invention 3 The composite material has excellent property of adjustable up-conversion luminescence. With UCNPs/CsPbX 3 (Br/I =1: 0.2,0.8. This is of great significance for further applications of the relevant upconversion luminescent device.
FIG. 5 shows UCNPs/CsPbBr in example 1 of the present invention 3 Time-resolved fluorescence attenuation spectrum of the composite material under excitation of 980nm pulse laser. Obtaining UCNPs/CsPbBr by exponential function fitting 3 The fluorescence lifetime of the composite was 0.7ms. The data show that after the two types of nanoparticles are hybridized, the excellent optical characteristics of the up-conversion nanoparticles and the perovskite nanocrystals are successfully interwoven together, and the intrinsic exciton life of the perovskite nanocrystals is prolonged from a nanosecond level to a millisecond level. For life time imagingAnd related devices such as infrared detection and the like, the invention has important significance for further application of UCNPs.
FIG. 6 (a) shows UCNPs/CsPbBr in example 1 of the present invention 3 Fluorescence intensity attenuation spectrum of the composite material film after a dripping experiment; FIG. 6 (b) shows UCNPs/CsPbBr in example 1 of the present invention 3 The fluorescence intensity attenuation spectrum of the @ UVCR composite film after a water dropping experiment. The figure clearly shows that the stability of the composite is greatly improved after coating by UVCR. UCNPs/CsPbBr 3 The @ UVCR composite material has strong environmental resistance and is simple and convenient to prepare. The invention has important significance for preparing the multimode anti-counterfeiting label with high stability
FIG. 7 shows UCNPs/CsPbBr in example 1 of the present invention 3 The dual-mode anti-counterfeiting diagram of the @ UVCR composite material. The invention designs a method for utilizing UCNPs/CsPbX 3 The @ UVCR composite material is used for anti-counterfeiting. In the figure, the L letter is UCNPs/CsPbBr 3 @ UVCR cladding, D letters by CsPbBr 3 @ UVCR coating. Under 980nm laser irradiation, the L letter fluoresces green, while the D letter fluoresces little. In contrast, under 365nm laser irradiation, LD letters can emit green fluorescence. The disappearance of D-letter fluorescence at 980nm excitation is due to the lack of UCNPs as an intermediate level to CsPbBr 3 The nanocrystals transfer energy. The luminescent color of the anti-counterfeiting label depends on CsPbBr 3 Intrinsic exciton emission of the nanocrystals. Under the UVCR package, the anti-counterfeit label has stronger environmental resistance, satisfies anti-counterfeit requirement.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. UCNPs/CsPbX 3 The composite material is characterized in that the UCNPs are nano materials with core-shell structures and doped Yb and Tm, and the CsPbX 3 Wherein X is Br and/or I, wherein Br: 1, 0.8, 0.4, 0.6。
2. The UCNPs/CsPbX of claim 1 3 The composite material is characterized in that the UCNPs have a structural formula of NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 。
3. The UCNPs/CsPbX of claim 2 3 The composite material is characterized in that in the crystal phase structure, UCNPs crystals are in a spherical core-shell hexagonal phase, csPbX 3 The crystal is cubic, and the CsPbX is 3 The crystal is close to the UCNPs crystal, and CsPbX is close to the UCNPs crystal 3 CsPbX with crystal size smaller than that far from the UCNPs crystal 3 The size of the crystals.
4. The UCNPs/CsPbX of claim 3 3 The composite material is characterized in that the preparation of the UCNPs comprises the following raw materials: y (CH) 3 CO 2 ) 3 ·H 2 O、Yb(CH 3 CO 2 ) 3 ·4H 2 O、Tm(CH 3 CO 2 ) 3 ·H 2 O, oleic acid, octadecene, NH-containing 4 F and NaOH in methanol.
5. The UCNPs/CsPbX of claim 3 3 Composite material, characterized in that the CsPbX is 3 The preparation method comprises the following steps: cs 2 CO 3 Octadecene, oleic acid, oleylamine and PbX 2 Wherein X is Br and/or I.
6. UCNPs/CsPbX as claimed in any of claims 1 to 5 3 The preparation method of the composite material is characterized in that the composite material is synthesized by adopting a high-temperature coprecipitation method and a thermal injection method, the first step adopts the high-temperature coprecipitation method to prepare the core-shell UCNPs nano particles, and the second step hot injects the core-shell UCNPs nano particles into CsPbX 3 During the synthesis of the nanocrystals.
7. The UCNPs/CsPbX of claim 6 3 The preparation method of the composite material is characterized by comprising the following steps:
(1) Nuclear NaYF 4 :Yb 3+ ，Tm 3+ The preparation of (1):
mixing raw material Y (CH) 3 CO 2 ) 3 ·H 2 O、Yb(CH 3 CO 2 ) 3 ·4H 2 O、Tm(CH 3 CO 2 ) 3 ·H 2 Placing O, oleic acid and octadecene in a flask, exhausting air and moisture, and dissolving solid powder; adding a solution containing NH 4 F and NaOH methanol solution, the temperature is set to be 45-55 ℃, the reaction is carried out under the circulation of protective atmosphere, the methanol and the water are removed, the temperature is raised to 250-350 ℃ for continuous reaction, after the reaction is finished, the heating is stopped, and the solution is cooled to the room temperature; adding ethanol into the solution, centrifuging to obtain a precipitate, repeatedly cleaning the precipitate, and finally dissolving the precipitate in cyclohexane;
(2) Core-shell NaYF 4 :Yb 3+ ,Tm 3+ @NaYF 4 The preparation of (1):
mixing raw material Y (CH) 3 CO 2 ) 3 ·H 2 Placing O, oleic acid and octadecylene in a flask, exhausting air and moisture, and dissolving solid powder; adding the NaYF prepared in the step (1) into the solution 4 :Yb 3+ ，Tm 3+ After stirring evenly, continuously adding the solution containing NH 4 F and NaOH methanol solution, the temperature is set to be 45-55 ℃, the reaction is carried out under the circulation of protective atmosphere, the methanol and the water are removed, the temperature is raised to 250-350 ℃ for continuous reaction, after the reaction is finished, the heating is stopped, and the solution is cooled to the room temperature; adding ethanol and cyclohexane into the solution, centrifuging to obtain a precipitate product, repeatedly cleaning the precipitate product, and finally dissolving the precipitate product in toluene;
(3)UCNPs/CsPbX 3 preparing a composite material:
(1) preparation of the precursor: mixing Cs 2 CO 3 Octadecylene and oleic acid are put in a container until the C is 2 CO 3 Completely dissolving to obtain a cesium salt precursor solution;
(2) PbX is reacted with 2 Placing with octadecene in a container, injecting oleic acid and octadecylene under protective atmosphereOleylamine, dissolving PbX 2 After the dissolution is finished, injecting the NaYF obtained in the step (2) 4 :Yb 3+ ,Tm 3+ @NaYF 4 Toluene solution, heating the solution to 150-180 deg.C, injecting cesium salt precursor solution obtained in the step (1), centrifuging the obtained product, and removing the supernatant to obtain UCNPs/CsPbBr 3 A composite material.
8. The UCNPs/CsPbX of claim 7 3 The preparation method of the composite material is characterized in that the protective atmosphere is nitrogen.
9. UCNPs/CsPbX as claimed in any of claims 1 to 5 3 The application of the composite material is characterized in that the composite material is used for preparing anti-counterfeiting materials.
10. The UCNPs/CsPbX of claim 9 3 The application of the composite material is characterized in that photosensitive resin is wrapped in UCNPs/CsPbX 3 Forming an anti-counterfeiting material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108795428A (en) * | 2018-06-20 | 2018-11-13 | 中国地质大学（北京） | A kind of anti-fake material and its preparation method and application |
| CN111909695A (en) * | 2019-05-07 | 2020-11-10 | 中国科学院福建物质结构研究所 | Rare earth up-conversion and perovskite quantum dot composite nanomaterial and preparation method and application thereof |
| CN113061434A (en) * | 2019-12-31 | 2021-07-02 | Tcl集团股份有限公司 | Perovskite quantum dot, preparation method thereof and photoelectric device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108795428A (en) * | 2018-06-20 | 2018-11-13 | 中国地质大学（北京） | A kind of anti-fake material and its preparation method and application |
| CN111909695A (en) * | 2019-05-07 | 2020-11-10 | 中国科学院福建物质结构研究所 | Rare earth up-conversion and perovskite quantum dot composite nanomaterial and preparation method and application thereof |
| CN113061434A (en) * | 2019-12-31 | 2021-07-02 | Tcl集团股份有限公司 | Perovskite quantum dot, preparation method thereof and photoelectric device |
Non-Patent Citations (2)
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| MIN ZENG等: "Strong upconversion emission in CsPbBr3 perovskite quantum dots through efficient BaYF5:Yb, Ln sensitization", . MATER. CHEM. C, vol. 7, pages 2014 - 2021 * |
| MINGXING LI等: "Multi-color UCNPs/CsPb(Br1−xIx)3 forupconversion luminescence and dual-modal anticounterfeiting", OPTICS EXPRESS, vol. 31, no. 2, pages 2956 - 2966 * |
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