CN116875301A - Multicolor adjustable afterglow silicon-based nano-dot, preparation method and application thereof - Google Patents
Multicolor adjustable afterglow silicon-based nano-dot, preparation method and application thereof Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 239000002096 quantum dot Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 19
- 239000012498 ultrapure water Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000003287 optical effect Effects 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical group CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 8
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical group Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 5
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 39
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- 238000010586 diagram Methods 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000002165 resonance energy transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
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- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
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- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04W—WIRELESS COMMUNICATION NETWORKS
- H04W12/00—Security arrangements; Authentication; Protecting privacy or anonymity
- H04W12/03—Protecting confidentiality, e.g. by encryption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Computer Security & Cryptography (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Inorganic Chemistry (AREA)
- Computer Networks & Wireless Communication (AREA)
- Signal Processing (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a multicolor adjustable afterglow silicon-based nano dot, a preparation method and application thereof, wherein the method comprises the following steps: s1, dissolving urea with ultrapure water, adding a precursor, and uniformly stirring; s2, reacting under heating, cooling to room temperature after the reaction is finished, grinding, washing and drying to obtain the multicolor adjustable afterglow silicon-based nano-dots; wherein the precursor is silane or a mixture of silane and rhodamine. The four multicolor silicon-based nano-dot afterglow materials are successfully prepared, the four materials have stable optical properties, and four different afterglow colors can be emitted under the same excitation light source (365 nm); the four materials can realize optical anti-counterfeiting and 5D information encryption based on afterglow emission characteristics after ultraviolet irradiation is closed, have the advantages of being multi-color adjustable, high in information encryption level and the like, and provide higher safety and more selectivity for anti-counterfeiting application.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a multicolor adjustable afterglow silicon-based nano dot, a preparation method and application thereof.
Background
The room temperature phosphorescent materials are widely used in information security, illumination, photocatalysis, biological imaging and other aspects due to their vivid phosphorescence characteristics. The traditional method for synthesizing the phosphorescent material mainly realizes the afterglow effect through an inorganic compound containing rare earth or a compound containing noble metal, thus inevitably causing the defects of high biotoxicity, high manufacturing cost and the like. Some samples even need to be cooled by liquid nitrogen to form a low-temperature rigid glass form so as to realize afterglow emission. The complexity of synthesis conditions is removed, and in the obtained phosphorescent material, molecular vibration and interference of oxygen molecules and water molecules are also non-negligible influence factors on triplet quenching phenomenon.
In the manufacturing process of the existing phosphorescent material, the multicolor adjustable phosphorescent material is widely focused due to the ingenious application of the multicolor adjustable phosphorescent material in the field of multidimensional information encryption. Compared with the defect that fluorescence emission is easy to imitate, the multi-dimensional encryption of information can be realized through the combination and collocation of various phosphorescence colors and different residual glow durations. However, most of the phosphorescent materials emit light near blue-green light, and the use of multicolor phosphorescent materials is severely limited by the lack of phosphorescent materials from yellow to red light emitting regions.
Multicolor phosphorescent materials implemented according to multicolor-emitted carbon nanodots make up for the defect of multicolor tunability, but a two-step synthesis method is generally required to fix the carbon nanodots in a composite matrix to achieve efficient phosphorescence. The two-step synthesis method involves mutual selection of a host and a guest and change of reaction conditions, increases uncontrollable risks, and simultaneously directly influences the production efficiency of the final product due to the uniformity of the initial product. It is necessary to explore a general synthetic strategy for multicolor tunable phosphorescent materials.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a multicolor adjustable afterglow silicon-based nano dot, a preparation method and application thereof aiming at the defects in the prior art. The invention synthesizes the multicolor tunable afterglow nanomaterial based on the silicon-based nano dot design, realizes the coverage range from cyan light to red light of the silicon-based nano dot afterglow nanomaterial, and can be applied to optical anti-counterfeiting and 5D information encryption according to afterglow time lengths of different colors.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving urea with ultrapure water, adding a precursor, and uniformly stirring;
s2, reacting under heating, cooling to room temperature after the reaction is finished, grinding, washing and drying to obtain the multicolor adjustable afterglow silicon-based nano-dots;
wherein the precursor is silane or a mixture of silane and rhodamine.
Preferably, the preparation method of the multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving urea with ultrapure water, adding a precursor, and uniformly stirring;
s2, reacting for 3-10 hours at 170-190 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol, and drying at 50-70 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dots.
Preferably, the preparation method of the multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 0.8-1.2g of urea with 10-40mL of ultrapure water, adding a precursor, and uniformly stirring;
s2, reacting for 3-10 hours at 170-190 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol, and drying at 50-70 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dots.
Preferably, the silane is N- (2-aminoethyl) -3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane, and the rhodamine is rhodamine 6G or rhodamine B.
Preferably, the preparation method of the multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of 3-aminopropyl triethoxysilane, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: C-Sinds@UA of cyan afterglow.
Preferably, the preparation method of the multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: yellow afterglow Y-Sinds@UA.
Preferably, the preparation method of the multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1G of urea with 20mL of ultrapure water, adding 1.0mL of 3-aminopropyl triethoxysilane (APTES) and 3.0mg of rhodamine 6G, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: orange afterglow O-Sinds@UA.
Preferably, the preparation method of the multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and 3.0mg of rhodamine B, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: R-Sinds@UA of red afterglow.
In a second aspect of the invention, there is provided a polychromatic tunable afterglow-based nanodot, prepared by the method as described above.
In a third aspect of the invention, an application of the multi-color adjustable afterglow silicon-based nano-dots in optical anti-counterfeiting and 5D information encryption is provided.
The beneficial effects of the invention are as follows:
the four multicolor silicon-based nano-dot afterglow materials are successfully prepared, the four materials have stable optical properties, and four different afterglow colors can be emitted under the same excitation light source (365 nm); the four materials can realize optical anti-counterfeiting and 5D information encryption based on afterglow emission characteristics after ultraviolet irradiation is closed, have the advantages of being multi-color adjustable, high in information encryption level and the like, and provide higher safety and more selectivity for anti-counterfeiting application; the synthesis system provided by the invention not only provides a general method for synthesizing full-color spectrum phosphorescence materials, but also has the advantages of nontoxic and environment-friendly raw materials, simple and quick reaction procedures, and can be popularized to mass production.
Drawings
FIG. 1 is a graph showing the results of structural property testing of four silicon-based nanodots prepared in examples 1-4 of the present invention;
FIG. 2 is a graph showing the results of optical property testing of four silicon-based nanodots prepared in examples 1-4 of the present invention under ultraviolet (365 nm) excitation;
FIG. 3 is a schematic diagram of the mechanism of afterglow emission process and phosphorescent resonance energy transfer of the silicon-based nanodots prepared by the invention;
FIG. 4 is a diagram showing the application of four silicon-based nanodots prepared in examples 1-4 of the present invention in optical anti-counterfeit and dual information encryption;
FIG. 5 is a diagram showing an example of an implementation of 5D information encryption for three afterglow materials Y-SiNDs@UA, O-SiNDs@UA and R-SiNDs@UA prepared in an embodiment of the invention.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
A preparation method of multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of 3-aminopropyl triethoxysilane, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: C-Sinds@UA of cyan afterglow.
Example 2
A preparation method of multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: yellow afterglow Y-Sinds@UA.
Example 3
A preparation method of multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1G of urea with 20mL of ultrapure water, adding 1.0mL of 3-aminopropyl triethoxysilane (APTES) and 3.0mg of rhodamine 6G, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: orange afterglow O-Sinds@UA.
Example 4
A preparation method of multicolor adjustable afterglow silicon-based nano-dots comprises the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and 3.0mg of rhodamine B, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: R-Sinds@UA of red afterglow.
The following performance tests and characterization were performed on the multi-color tunable afterglow silicon-based nanodots prepared in examples 1 to 4
(1) Structural properties
Referring to fig. 1, structural property test results of four silicon-based nanodots prepared in examples 1 to 4;
from TEM pictures of four silicon-based nanodots, FIGS. 1a-1d, it can be seen that the four materials are each composed of relatively uniform size near-spherical particles. FIG. 1e shows XPS analysis results of four silicon-based nano-dot phosphorescent materials, demonstrating the presence of four elements, C, N, O and Si, in all four materials. FIG. 1f is a FT-IR spectrum of four silicon-based nano-dot phosphorescent materials, the presence of Si-O, si-C bonds laying a structural foundation for the phosphorescent properties of the materials.
(2) Optical Properties
Referring to FIG. 2, the results of the optical property test of the four silicon-based nanodots prepared in examples 1-4 under ultraviolet (365 nm) excitation are shown;
as can be seen from FIGS. 2a-b, the fluorescence emission peak of C-Sinds@UA under 365nm ultraviolet excitation is located at 425nm, and the afterglow emission peak is located at 520nm; the fluorescence emission peak of Y-SiNDs@UA under 365nm ultraviolet excitation is 450nm, and the afterglow emission peak is 555nm; the fluorescence emission and afterglow emission peaks of O-SiNDs@UA under the excitation of 365nm ultraviolet light are both at 575nm; the fluorescence emission and afterglow emission peaks of R-SiNDs@UA under the excitation of 365nm ultraviolet light are all located at 605nm. Fig. 2c shows the afterglow luminescence of four phosphorescent materials under visual inspection. The persistence durations of the four materials after turning off the uv were 13, 12,8 and 6s, respectively.
(3) Mechanism of afterglow luminescence
Referring to FIG. 3, an afterglow emission process mechanism and phosphorescence resonance energy transfer diagram of the silica-based nanodots prepared by the invention are shown;
in the hydrothermal reaction process, silane participates in the recrystallization process of urea and generates silicon nano-dots in situ (figure 3 a), and meanwhile, new functional groups are introduced into the nano-composite by the intervention of silane, so that new surface states are generated, and the specific expression of different silanes corresponds to different phosphorescence emission wavelengths. Furthermore, the Si-C and Si-O bonds in the nanocomposite play an important role in reducing phosphorescent non-radiative relaxation. It is noted that the fluorescence and afterglow emission wavelength positions of the two materials of O-Sinds@UA and R-Sinds@UA are the same, and the phenomenon accords with the luminescence principle of phosphorescence resonance energy transfer (figure 3 b), namely under the condition of fluorescence irradiation, the fluorescence of an energy acceptor in a compound is excited by a light source and a silicon nano point, after excitation disappears, the afterglow of the silicon nano point serves as an energy transfer donor, and the energy acceptor in the compound is continuously excited to emit orange afterglow and red afterglow respectively.
(4) Application performance test of polychromatic adjustable afterglow silicon-based nano-dots in optical anti-counterfeiting and double information encryption
Referring to fig. 4, an example diagram of the application of the four silicon-based nanodots prepared in examples 1-4 in optical anti-counterfeiting and dual information encryption is shown.
FIG. 4a shows the use of four colors of material to design a butterfly pattern, the four colors and their corresponding butterfly pattern portions being clearly visible when the ultraviolet light source (365 nm) is extinguished, demonstrating the information carrying and transmitting effect of the four afterglow materials; in fig. 4b, C-sinds@ua with phosphorescent properties and SiNDs without phosphorescent properties are filled into the mold, respectively, all materials are white under sunlight, and emit the same blue fluorescence under ultraviolet irradiation, so that correct information cannot be read. When the ultraviolet irradiation is turned off, fluorescence of the material having no phosphorescent property disappears as excitation disappears. Whereas C-sinds@ua exhibits stable phosphorescent properties, i.e. after excitation is turned off, the material exhibits a pronounced cyan afterglow, while exhibiting four encrypted alphabetic messages "USTC".
Fig. 4c shows that dual information encryption is achieved using different colors of after-glowing material. The pattern adopts three materials: C-Sinds@UA, Y-Sinds@UA and O-Sinds@UA. Cyan represents the common information, yellow represents the unique color of code 1, and orange represents the unique color of code 2. After reading the cyan and yellow combination, the correct information code 1 (CHEMISTRY) is obtained. The combination of cyan and orange results in information code 2 (CHOCOLATE) in a similar manner.
Referring to FIG. 5, an exemplary diagram of an application of three afterglow materials Y-SiNDs@UA, O-SiNDs@UA and R-SiNDs@UA to achieve 5D information encryption is shown.
By observing the phosphorescence spectrum of the material, the Y-SiNDs@UA and O-SiNDs@UA still have partial phosphorescence intensity at the position larger than 600nm, and multiple information encryption with the same color but different residual glow durations can be skillfully realized by combining red light emission of R-SiNDs@UA at 600nm and using a filter with the transmission wavelength of 600 nm.
As shown in fig. 5a, the security model does not show unique features under sunlight and uv irradiation, and still shows a mixed color when the uv irradiation is turned off, identified as "False" on a computer. And after the optical filter is added, the afterglow shows uniform red, which can be identified as True. Based on the phenomenon, higher-level 5D information encryption can be realized on the basis of multiple anti-counterfeiting.
As shown in fig. 5b, the encryption information is encoded based on the mousse codebook by using three materials of Y-sinds@ua, O-sinds@ua and R-sinds@ua, and only the wrong code 1 and code 2 can be obtained in the ultraviolet light or the off state due to the lack of the help of the optical filter. After adding the filter, the correct code 3"BLUEBERRY" can be read out first under the condition of turning off the ultraviolet light. Because the three materials have different afterglow time lengths in the red light area, the Y-Sinds@UA disappears firstly in the red light area due to the lowest intensity after 2s, and the code 4 'BANANA' is displayed. Also, the color of O-SiNDs@UA disappeared after 4 seconds, showing the code 5"DATE", since the red light intensity was lower than R-SiNDs@UA. The anti-counterfeiting strategy can only obtain interference information under ultraviolet irradiation and afterglow modes, and correct encrypted content can be read only with the aid of the optical filter, so that the correct information can be better hidden.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The preparation method of the multicolor adjustable afterglow silicon-based nano-dot is characterized by comprising the following steps of:
s1, dissolving urea with ultrapure water, adding a precursor, and uniformly stirring;
s2, reacting under heating, cooling to room temperature after the reaction is finished, grinding, washing and drying to obtain the multicolor adjustable afterglow silicon-based nano-dots;
wherein the precursor is silane or a mixture of silane and rhodamine.
2. The method for preparing the multi-color adjustable afterglow silicon-based nano-dots according to claim 1, comprising the following steps:
s1, dissolving urea with ultrapure water, adding a precursor, and uniformly stirring;
s2, reacting for 3-10 hours at 170-190 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol, and drying at 50-70 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dots.
3. The method for preparing the multi-color adjustable afterglow silicon-based nano-dots according to claim 2, comprising the steps of:
s1, dissolving 0.8-1.2g of urea with 10-40mL of ultrapure water, adding a precursor, and uniformly stirring;
s2, reacting for 3-10 hours at 170-190 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol, and drying at 50-70 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dots.
4. The method for preparing the polychromatic adjustable afterglow silicon-based nano dots according to claim 2, wherein the silane is N- (2-aminoethyl) -3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane, and the rhodamine is rhodamine 6G or rhodamine B.
5. The method for preparing the multi-color adjustable afterglow silicon-based nano-dots according to claim 4, comprising the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of 3-aminopropyl triethoxysilane, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: C-Sinds@UA of cyan afterglow.
6. The method for preparing the multi-color adjustable afterglow silicon-based nano-dots according to claim 4, comprising the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: yellow afterglow Y-Sinds@UA.
7. The method for preparing the multi-color adjustable afterglow silicon-based nano-dots according to claim 4, comprising the following steps:
s1, dissolving 1G of urea with 20mL of ultrapure water, adding 1.0mL of 3-aminopropyl triethoxysilane (APTES) and 3.0mg of rhodamine 6G, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: orange afterglow O-Sinds@UA.
8. The method for preparing the multi-color adjustable afterglow silicon-based nano-dots according to claim 4, comprising the following steps:
s1, dissolving 1g of urea with 20mL of ultrapure water, adding 1.0mL of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and 3.0mg of rhodamine B, and uniformly stirring;
s2, reacting for 5 hours at 180 ℃, cooling to room temperature after the reaction is finished, grinding, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain the multicolor adjustable afterglow silicon-based nano-dot: R-Sinds@UA of red afterglow.
9. A multi-color adjustable afterglow silicon-based nanodot, characterized in that it is prepared by the method according to any one of claims 1 to 8.
10. Use of the multi-color adjustable afterglow silicon-based nanodots according to claim 9 for optical anti-counterfeiting and 5D information encryption.
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