CN111476333B - Ln-MOF-based multicolor heterojunction miniature intelligent response photon anti-counterfeiting bar code material, device, preparation and application - Google Patents

Ln-MOF-based multicolor heterojunction miniature intelligent response photon anti-counterfeiting bar code material, device, preparation and application Download PDF

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CN111476333B
CN111476333B CN202010253117.6A CN202010253117A CN111476333B CN 111476333 B CN111476333 B CN 111476333B CN 202010253117 A CN202010253117 A CN 202010253117A CN 111476333 B CN111476333 B CN 111476333B
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epitaxial structure
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bar code
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CN111476333A (en
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高振华
孟宪赓
许宝源
王雪
王子飞
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Qilu University of Technology
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Abstract

The invention relates to a Ln-MOF-based multicolor heterojunction miniature intelligent response photon anti-counterfeiting bar code material, a device, preparation and application thereof, wherein the material comprises a seed module and an epitaxial structure, and the seed module and the epitaxial structure are Eu 3+ Composite Ln-MOF micron rod crystal material formed by doping Tb-BTC micron rod crystal, and different Eu grows on the structure of seed module 3+ And doping concentration of the epitaxial structure to form a responsive heterostructure. The invention constructs a heterostructure based on multicolor Ln-MOF by adopting a step-by-step epitaxial growth method, and controls energy transfer among different Ln ions through thermal stimulation. The emission color of the temperature control and the emission peak with good resolution form the inherent fingerprint of the heterostructure, and can be used for preparing the responsive photon bar code, which remarkably enhances the safety and expands the coding capacity.

Description

Ln-MOF-based multicolor heterojunction miniature intelligent response photon anti-counterfeiting bar code material, device, preparation and application
Technical Field
The invention relates to the technical field of optical anti-counterfeiting devices, in particular to a photon bar code material and a device which have anti-counterfeiting function through intelligent response multicolor micro-nano heterogeneous structure, and preparation and application thereof.
Background
Micro-nano-photonic barcodes are of great interest for their great potential in multiplex biological analysis, commodity tracking and information security. The micro-nano multicolor luminous heterojunction can be easily distinguished by a visually identifiable pattern, so that the micro-nano multicolor luminous heterojunction has great potential in the field of constructing photon bar codes. However, current micro-nano multi-color heterojunctions output static luminescence signals, and data or information in these bar codes are usually visible under ultraviolet or near infrared excitation, thus cannot guarantee practical application in information protection. Compared with a static bar code, the micro intelligent response luminescence heterojunction can spatially perform color conversion under external stimulus, so that the micro intelligent response luminescence heterojunction has wide development prospect in the aspects of information encryption and anti-counterfeiting. However, there are great difficulties in the preparation of micro-nano intelligent response luminescence heterojunction at present. Chinese patent document CN110295038A discloses a rare earth/quantum dot composite up-conversion luminescent material, and preparation method and application thereof. The composite material consists of a rare earth up-conversion luminescent material and quantum dots, and can realize high-efficiency up-conversion luminescence in a full visible spectrum by regulating and controlling the types and the proportion of the rare earth up-conversion luminescent material and the quantum dots, however, the luminescent material lacks responsiveness, limits the application of the luminescent material in a micro-nano optical platform, and has a reversible and lossless intelligent response micro-nano structure at present, which is rarely reported; in addition, even though these smart response structures are well implemented, how to integrate multiple smart response modules into micro-nano heterojunctions still faces very big challenges due to lattice mismatch between different luminescent materials, thus limiting their deep anti-counterfeit application as advanced security tags.
Photonic metal-organic framework compounds (MOFs) can provide abundant optical coding elements as a crystalline material constructed from luminescent organic ligands and metal ions, thereby providing an excellent system for the preparation of micro-nano multi-color barcodes. In addition, the interaction among different optical elements in the MOFs structure can be easily regulated and controlled by external environmental stimulus, so that great flexibility is brought to the realization of the response type optical module. Meanwhile, the excellent compatibility of MOFs enables the MOFs to prepare heterogeneous nanostructures, so that different intelligent response modules are integrated in the micro-nano heterojunction. Wherein the lanthanide metals (Ln) have similar coordination chemistry and sharp and easily-identified emission peaks, and can establish an excellent Ln-MOFs system with multicolor heterogeneous emission. Thus, the Ln-MOF heterostructure will provide an innovative coding scheme for the development of smart-responsive multicolor bar codes.
At present, the miniature intelligent response photon anti-counterfeiting bar code material and device based on lanthanide series metal-organic framework multi-color heterojunction have not been reported too much, and therefore, the invention is provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a Ln-MOF multi-color heterojunction-based miniature intelligent response photon anti-counterfeiting bar code material, a device, preparation and application.
The technical scheme of the invention is as follows:
a miniature intelligent response photon anti-counterfeiting bar code material based on Ln-MOF multi-color heterojunction comprises a seed module and an epitaxial structure, wherein the seed module and the epitaxial structure are Eu 3+ Composite Ln-MOF micron rod crystal material formed by doping Tb-BTC micron rod crystal, and different Eu grows on the structure of seed module 3+ And doping concentration of the epitaxial structure to form a responsive heterostructure. Namely: eu of the present invention 3+ Doped into the Tb-BTC, replacing part Tb.
According to the invention, preferably, the seed module and the epitaxial structure comprise the following chemical compositions in molar ratio:
Ln(NO 3 ) 3 ·6H 2 O:C 9 H 6 O 6 (BTC)＝0.001-0.02:0.01-0.1。
according to the invention, it is preferred that Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3+ The mol percentage is that x is more than or equal to 0 and less than or equal to 100, ln (NO 3 ) 3 ·6H 2 Ln (NO) of O-neutralized epitaxial structure 3 ) 3 ·6H 2 In O, x cannot be simultaneously 0, and x cannot be simultaneously 100.
According to the invention, preferably, the seed module Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3 + Mole percent, 0<x<100; ln (NO) of said epitaxial structure 3 ) 3 ·6H 2 In O, ln 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, 0<x<100。
According to the invention, preferably, the seed module Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3 + Mole percent, 0<x<100; ln (NO) of said epitaxial structure 3 ) 3 ·6H 2 In O, ln 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, x=0 or 100.
According to the invention, preferably, the seed module Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3 + Mole percent, x=0 or 100; ln (NO) of said epitaxial structure 3 ) 3 ·6H 2 In O, ln 3+ Is x% Eu 3+ And (1-x%) Tb 3 + Mole percent, 0<x<100。
The invention relates to a response MOF heterojunction material realized by multi-step epitaxial growth, the response position of which is Eu 3+ The composite Ln-MOF micron rod crystal material formed by doping Tb-BTC micron rod crystal can be divided into seed modules and epitaxial structures, and different Eu grows on the seed module structure 3+ And doping concentration of the epitaxial structure to form a responsive heterostructure. By carrying out external stimulation on the heterojunction MOF, the control of energy transfer between different Ln ions is realized, so that the luminous color of different sections of the material is influenced, the characteristic emission spectrum of different sections is spectrally reflected, and therefore, the heterojunction MOF can be edited into a photon bar code according to different characteristics of the spectrum, for example: fig. 1 is a possible bar code encoding rule, and fig. 2 is a spectral signature of an edited bar code material. Eu by changing the response position 3+ The ion doping concentration and the thermal stimulation are combined to finally realize the intelligent response of the space color. Eu of the present invention 3+ Doped into Tb-BTC micron rod crystal, eu 3+ The replacement portion Tb can achieve a stimulated photon response. I.e. the spectrum changes after thermal stimulation. No Eu 3+ Doping to obtain Tb-BTC or Eu 3+ Eu-BTC is obtained by 100% doping, and the spectrum is unchanged after thermal stimulation.
According to the invention, the preparation method of the seed module comprises the following steps:
ln (NO) is weighed according to the mole ratio 3 ) 3 ·6H 2 Placing O and BTC in a glass bottle, adding N, N-Dimethylformamide (DMF) and deionized water (H) 2 And O) carrying out high-temperature reaction, and washing the product to obtain colorless rod-like crystals which are the seed modules.
According to the present invention, it is preferable that the aspect ratio of the seed crystals produced is (10-70 μm): (1-20) μm.
According to the invention, the reaction temperature is preferably 50-120 ℃; preferably, the reaction time is 80-280min.
According to the invention, preference is given to DMF and H 2 The volume ratio of O is 1:0.2-0.8.
According to the invention, it is preferred that Ln (NO 3 ) 3 ·6H 2 The volume ratio of the O molar quantity to the N, N-dimethylformamide is 1: (0.4-1.1) mmol/L.
According to the invention, the preparation method of the epitaxial structure adopts a step-by-step epitaxial growth method and comprises the following steps:
ln (NO) is weighed according to the mole ratio 3 ) 3 ·6H 2 Placing O and BTC in a glass bottle, adding N, N-Dimethylformamide (DMF) and deionized water (H) 2 O), adding different Eu 3+ The seed module crystal with ion doping amount is subjected to high-temperature reaction, and the colorless rod-shaped crystal obtained after washing the product is the miniature intelligent response photon anti-counterfeiting bar code material based on Ln-MOF multicolor heterojunction. Namely: different Eu are grown on the structure of the seed module by adopting a step-by-step epitaxial growth method 3+ And an epitaxial structure with ion doping concentration to form a responsive heterostructure.
According to the present invention, it is preferable that the resultant hetero-crystalline has an aspect ratio of (30-100) μm: (1-20) μm.
According to the invention, the miniature intelligent response photon anti-counterfeiting bar code device based on lanthanide metal-organic framework multicolor heterojunction comprises a heterostructure formed by the seed module and the epitaxial module and a carrier, wherein the carrier provides a stimulation means for the response type structure, and the miniature intelligent response photon anti-counterfeiting bar code device is obtained by combining the heterostructure with the carrier.
According to the invention, preferably, the carrier is a heating module.
According to the present invention, the response sites are divided into seed modules and epitaxial structures, when Eu for seed modules and epitaxial structures 3+ When the doping amount of ions is different, under the thermal stimulation, the energy transfer between different lanthanide ions in Ln-BTC micron rod crystal is also different, so that under the excitation of excitation light with specific wavelength, different emission colors can be displayed on different doping concentrations of heterojunction, corresponding changes can be displayed on the spectrum, obvious stimulus response is displayed, and different Eu is displayed 3+ The characteristic spectrum of the composite Ln-MOF micron rod crystal material with ion doping concentration is shown in figure 3. A specific heterostructure is shown in fig. 4, and the characteristic spectral change under thermal stimulus is shown in fig. 5 and 6.
According to the invention, the application of the lanthanide series metal-organic framework polychromatic heterojunction-based miniature intelligent response photon anti-counterfeiting bar code device is applied as a highly integrated intelligent response miniature device in the fields of data encryption and decryption, information security anti-counterfeiting and energy conversion.
The invention provides an intelligent response center formed by using lanthanide metal-organic framework polychromatic heterojunction materials which are easy to prepare and low in cost, and the Eu in a seed module and an epitaxial module is effectively controlled by heating as a stimulation means 3+ The doping amount of the photonic anti-counterfeiting bar code device can be used for constructing a miniature intelligent response type multicolor heterojunction photonic anti-counterfeiting bar code device. The result shows that the device has excellent performance and low cost, and can be well applied to the fields of optical communication, information encryption or high-end anti-counterfeiting.
The principle of the invention is as follows:
the invention replaces the traditional static photon anti-counterfeiting bar code with the response photon anti-counterfeiting bar code based on lanthanide MOF, and under the heating condition, the Eu is different 3+ The energy transfer states inside Ln-MOF crystals with ion doping amount are different, and BTC is used as an organic ligand of an MOF structure, so that the BTC not only can be used as a sensitizer to assist Ln-MOF to emit light, but also can be used for establishing a bridge effect for energy transfer among different lanthanide ions according to the proper size. Therefore, the intelligent response type photon anti-counterfeiting bar code device with excellent optical performance can be obtained. The invention has similarity to allDevices capable of energy transfer, both in terms of coordination chemistry and characteristic emission peaks, are suitable.
The invention has the functions of the raw materials: ln (NO) 3 ) 3 ·6H 2 O provides metal node Eu of MOF structure 3+ And Tb 3+ BTC (trimesic acid) is an organic ligand, plays roles in sensitizing Ln-MOF luminescence and transferring energy between ions in the MOF, and a heating module is used as a stimulation means to jointly form a photon response module with stimulation responsiveness with other parts under the excitation of specific wavelength.
The beneficial effects of the invention are as follows:
the invention constructs a heterostructure based on multicolor Ln-MOF by adopting a step-by-step epitaxial growth method, and controls energy transfer among different Ln ions through thermal stimulation. The emission color of the temperature control and the emission peak with good resolution form the inherent fingerprint of the heterostructure, and can be used for preparing the responsive photon bar code, which remarkably enhances the safety and expands the coding capacity. The invention can provide a new way for constructing intelligent response type devices in the fields of data recording and information security.
Drawings
FIG. 1 is a coding rule of the invention compiled into a photon bar code according to different characteristics of spectra.
Fig. 2 is a spectral signature of the encoded barcode material of the present invention.
FIG. 3 shows different Eu values according to the present invention 3+ Characteristic spectrum diagram of composite Ln-MOF micron rod crystal material with doping concentration.
FIG. 4 is a schematic diagram of a Ln-MOF-based multicolor heterojunction according to the present invention.
Fig. 5 and 6 are characteristic spectrum change diagrams of different heterostructures under thermal stimulus.
Detailed Description
The invention is further described below with reference to the drawings and the detailed description, but is not limited thereto.
The ion doping concentrations in the examples are all mole percent.
Miniature intelligent response photon anti-counterfeiting strip based on Ln-MOF multi-color heterojunctionThe shape code material comprises a seed module and an epitaxial structure, wherein the seed module and the epitaxial structure are Eu 3+ Ion doped into Tb-BTC micron rod crystal to form composite Ln-MOF micron rod crystal material, and different Eu are grown on the seed module structure 3+ And an epitaxial structure with ion doping concentration to form a responsive heterostructure. The seed module and the epitaxial structure comprise the following raw materials in percentage by mole:
Ln(NO 3 ) 3 ·6H 2 O:C 9 H 6 O 6 (BTC)＝0.001-0.02:0.01-0.1。Ln(NO 3 ) 3 ·6H 2 ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3+ X is more than or equal to 0 and less than or equal to 100 in mole percent;
ln (NO) of seed module 3 ) 3 ·6H 2 Ln (NO) of O-neutralized epitaxial structure 3 ) 3 ·6H 2 In O, x cannot be simultaneously 0, and x cannot be simultaneously 100. Preferably, the seed module Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3 + Mole percent, 0<x<100; ln (NO) of epitaxial structure 3 ) 3 ·6H 2 In O, ln 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, 0<x<100。
The preparation method of the seed module comprises the following steps:
ln (NO) is weighed according to the mole ratio 3 ) 3 ·6H 2 Placing O and BTC in a glass bottle, adding N, N-Dimethylformamide (DMF) and deionized water (H) 2 And O) carrying out high-temperature reaction, and washing the product to obtain colorless rod-like crystals which are the seed modules. Preferably, the resulting seed crystals have an aspect ratio of (10-70) μm: (1-20) μm. Preferably, the reaction temperature is 50-120 ℃ and the reaction time is 80-280min. Preferably, DMF and H 2 The volume ratio of O is 1:0.2-0.8. Preferably, ln (NO 3 ) 3 ·6H 2 The volume ratio of the O molar quantity to the N, N-dimethylformamide is 1: (0.4-1.1) mmol/L.
The preparation method of the epitaxial structure adopts a step-by-step epitaxial growth method and comprises the following steps:
ln (NO) is weighed according to the mole ratio 3 ) 3 ·6H 2 Placing O and BTC in a glass bottle, adding N, N-Dimethylformamide (DMF) and deionized water (H) 2 O), adding different Eu 3+ The seed module crystal with ion doping amount is subjected to high-temperature reaction, and the colorless rod-shaped crystal obtained after washing the product is the miniature intelligent response photon anti-counterfeiting bar code material based on Ln-MOF multicolor heterojunction. Namely: different Eu are grown on the structure of the seed module by adopting a step-by-step epitaxial growth method 3+ And an epitaxial structure with ion doping concentration to form a responsive heterostructure. Preferably, the resulting heterojunction crystals have an aspect ratio of (30-100) μm: (1-20) μm.
Example 1
The material heterostructure composition of this embodiment is: seed module is 2% Eu 3+ Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystal, and the epitaxial structure is 5% Eu 3+ And the ions are doped into Ln-MOF micron rod crystal materials formed by Tb-BTC micron rod crystals.
Combining the heterostructure with a heating module to obtain the miniature intelligent response photon anti-counterfeiting bar code device. The heating module is a carrier and provides a stimulation means for the responsive structure, and the heterostructure is combined with the carrier. The characteristic segment spectrum changes obviously after thermal stimulation.
Example 2
The material heterostructure composition of this embodiment is: seed module 1% Eu 3+ Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystal, and the epitaxial structure is 3% Eu 3+ And the ions are doped into Ln-MOF micron rod crystal materials formed by Tb-BTC micron rod crystals.
Combining the heterostructure with a heating module to obtain the miniature intelligent response photon anti-counterfeiting bar code device. The characteristic segment spectrum changes obviously after thermal stimulation.
Example 3
The material heterostructure composition of this embodiment is: seed module 1.5% Eu 3+ Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystal, and the epitaxial structure is 4% Eu 3+ And the ions are doped into Ln-MOF micron rod crystal materials formed by Tb-BTC micron rod crystals.
Combining the heterostructure with a heating module to obtain the miniature intelligent response photon anti-counterfeiting bar code device. The characteristic segment spectrum changes obviously after thermal stimulation.
Example 4
The material heterostructure composition of this embodiment is: seed module 1.5% Eu 3+ Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystal, and the epitaxial structure is 0Eu 3+ And the ions are doped into Ln-MOF micron rod crystal materials formed by Tb-BTC micron rod crystals.
Combining the heterostructure with a heating module to obtain the miniature intelligent response photon anti-counterfeiting bar code device. The characteristic section spectrum of the seed module is obviously changed after thermal stimulation, and the epitaxial structure spectrum is not obviously changed.
Example 5
The material heterostructure composition of this embodiment is: seed module 1.5% Eu 3+ Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystal, and the epitaxial structure is 100% Eu 3+ The Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystals, namely the Eu-BTC micron rod crystals are of an epitaxial structure.
Combining the heterostructure with a heating module to obtain the miniature intelligent response photon anti-counterfeiting bar code device. The characteristic section spectrum of the seed module is obviously changed after thermal stimulation, and the epitaxial structure spectrum is not obviously changed.
Comparative example 1
The comparative example material is a Tb-BTC micron rod crystal material.
The material is combined with a heating module, and the characteristic section spectrum is not changed obviously after thermal stimulation.
Comparative example 2
The comparative example material is Eu-BTC micro rod crystal material.
The material is combined with a heating module, and the characteristic section spectrum is not changed obviously after thermal stimulation.
Comparative example 3
The heterostructure composition of the material of the comparative example is as follows: seed module 0Eu 3+ Tb-BTC micron rod crystal material formed by doping ions into Tb-BTC micron rod crystal, and the epitaxial structure is 100% Eu 3+ The Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystals, namely the Eu-BTC micron rod crystals are of an epitaxial structure.
The heterostructure is combined with a heating module, and the characteristic segment spectrum is not changed obviously after thermal stimulation.
Comparative example 4
The heterostructure composition of the material of the comparative example is as follows: seed module of 100% Eu 3+ Ln-MOF micron rod crystal material formed by doping ions into Tb-BTC micron rod crystal, namely Eu-BTC micron rod crystal is used as seed module, and the epitaxial structure is 0Eu 3+ And the ions are doped into Tb-BTC micron rod crystal materials formed by Tb-BTC micron rod crystals.
The heterostructure is combined with a heating module, and the characteristic segment spectrum is not changed obviously after thermal stimulation.

Claims (10)

1. A miniature intelligent response photon anti-counterfeiting bar code material based on Ln-MOF multi-color heterojunction is characterized by comprising a seed module and an epitaxial structure, wherein the seed module and the epitaxial structure are Eu 3+ Composite Ln-MOF micron rod crystal material formed by doping Tb-BTC micron rod crystal, and different Eu grows on the structure of seed module 3+ Doping concentration epitaxial structure to form response heterostructure;
the seed module and the epitaxial structure comprise the following raw materials in percentage by mole:
Ln(NO 3 ) 3 ·6H 2 O:C 9 H 6 O 6 (BTC)=0.001-0.02:0.01-0.1；
Ln(NO 3 ) 3 ·6H 2 ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Molar (mol)The percentage of the Ln (NO) of the seed module is more than or equal to 0 and less than or equal to 100 3 ) 3 ·6H 2 Ln (NO) of O-neutralized epitaxial structure 3 ) 3 ·6H 2 In O, x cannot be simultaneously 0, and x cannot be simultaneously 100.
2. The Ln-MOF multi-color heterojunction based miniature intelligent response photon anti-counterfeiting bar code material of claim 1, wherein the seed module Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, 0<x<100; ln (NO) of said epitaxial structure 3 ) 3 ·6H 2 In O, ln 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, 0<x<100。
3. The Ln-MOF multi-color heterojunction based miniature intelligent response photon anti-counterfeiting bar code material of claim 1, wherein the seed module Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, 0<x<100; ln (NO) of said epitaxial structure 3 ) 3 ·6H 2 In O, ln 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, x=0 or 100;
alternatively, the seed module Ln (NO 3 ) 3 ·6H 2 Ln in O 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, x=0 or 100; ln (NO) of said epitaxial structure 3 ) 3 ·6H 2 In O, ln 3+ Is x% Eu 3+ And (1-x%) Tb 3+ Mole percent, 0<x<100。
4. The method for preparing the seed module of claim 1, comprising the steps of:
ln (NO) is weighed according to the mole ratio 3 ) 3 ·6H 2 Placing O and BTC in a glass bottle, adding N, N-dimethylformamide%DMF) and deionized water (H 2 And O) carrying out high-temperature reaction, and washing the product to obtain colorless rod-like crystals which are the seed modules.
5. The method of claim 4, wherein the seed module crystals produced have an aspect ratio of (10-70): (1-20) μm.
6. The method for preparing a seed module according to claim 4, wherein the reaction temperature is 50-120 ℃ and the reaction time is 80-280min.
7. The method of preparing a seed module according to claim 4, wherein DMF and H 2 The volume ratio of O is 1:0.2-0.8, ln (NO) 3 ) 3 ·6H 2 The volume ratio of the O molar quantity to the N, N-dimethylformamide is 1: (0.4-1.1) mmol/L.
8. The method for preparing an epitaxial structure according to claim 1, which adopts a step-by-step epitaxial growth method, comprises the following steps:
ln (NO) is weighed according to the mole ratio 3 ) 3 ·6H 2 Placing O and BTC in a glass bottle, adding N, N-Dimethylformamide (DMF) and deionized water (H) 2 O), adding different Eu 3+ And (3) carrying out high-temperature reaction on the seed module crystal with ion doping amount, washing the product to obtain a colorless rod-shaped crystal, and realizing epitaxial structure growth to obtain the miniature intelligent response photon anti-counterfeiting bar code material based on Ln-MOF multi-color heterojunction.
9. A miniature intelligent response photon anti-counterfeiting bar code device based on lanthanide metal-organic framework multi-color heterojunction, which comprises a response type heterostructure formed by a seed module and an epitaxial structure according to any one of claims 1-3 and a carrier, wherein the carrier provides a stimulation means for the response type heterostructure, and the miniature intelligent response photon anti-counterfeiting bar code device is obtained by combining the response type heterostructure with the carrier.
10. The application of the lanthanide series metal-organic framework multicolor heterojunction-based miniature intelligent response photon anti-counterfeiting bar code device as a highly integrated intelligent response miniature device in the fields of data encryption and decryption, information security anti-counterfeiting and energy conversion.
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