CN113772716A - Method for rapidly preparing rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ - Google Patents
Method for rapidly preparing rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ Download PDFInfo
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- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
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Abstract
The invention discloses a method for rapidly preparing a rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ, which utilizes the plasmon thermal effect of a noble metal nano structure, takes a small-size gold nano island structure with a large absorption interface as a heat source, and leads the gold nano island structure to generate extremely high temperature in a very short time under the action of an external light field of resonance wavelength and transmit the extremely high temperature to a rare earth luminescent material so as to instantly raise the local temperature; meanwhile, thermal electrons generated by surface plasmon relaxation catalyze oxygen molecules adsorbed on the surface of the luminescent material to activate the oxygen molecules, so that the luminescent material is promoted to generate oxidation reaction, and the luminescent material is instantaneously transformed into rare earth oxide under the dual actions of instantaneous high temperature and activated oxygen. The invention utilizes the surface plasmon thermal effect to realize the preparation of the heterojunction micro-nano material combined by the rare earth fluoride and the rare earth oxide which are not matched with the crystal lattices on the level of single particles, the method is simple and easy to implement, the room temperature condition can be carried out, the reaction time is short, and the power density of the required exciting light is small.
Description
Technical Field
The invention belongs to the technical field of preparation of rare earth ion doped inorganic heterojunction luminescent materials, and particularly relates to a method for rapidly preparing a heterostructure micro-nano material in situ by combining rare earth fluoride and oxide.
Background
In recent years there has been an increasing interest in developing combinations of two or more materials with different properties to produce heterostructure materials with a combination of advantages, desirable dimensions, morphology and functionality. Rare earth ion-doped fluorinated materials are widely used in various fields such as three-dimensional displays, solar photoelectric conversion, optical information transfer, solid laser materials, fluorescent probes, and the like, by virtue of their superior and unique fluorescent characteristics. The rare earth oxide material has the advantages of good chemical stability, thermal stability (the melting point is higher than 2000 ℃), low toxicity and the like, and is widely applied to many fields of biology, medicine, electronic devices and the like. Therefore, the method combines the comprehensive advantages of rare earth fluoride and oxide micro-nano materials to prepare a single heterostructure at a single particle level, and the heterostructure not only has the efficient light-emitting characteristic of a fluorinated material, but also has the physical and chemical stability and the thermal stability of an oxide material. However, the preparation of the heterojunction micro-nano material must meet some strict requirements: 1. crystal structure matching 2, lattice parameter matching 3, and reaction temperature and conditions are similar. Due to reaction temperature and lattice mismatch, rare earth oxides will not be able to grow epitaxially on rare earth fluoride materials.
In recent years, many researches on preparation methods of heterojunction micro-nano materials with lattice mismatching have been carried out, and the preparation technologies include epitaxial growth, surface polymerization, mechanical hot melting and the like. But the heterojunction materials prepared by these methods all have their disadvantages. For example, luminescence quenching occurs due to the presence of surface defects, optical stability is poor, the preparation process is complicated, and the like. Therefore, the method overcomes the difficulties and technical bottlenecks of the conventional method, quickly and accurately obtains the heterojunction micro-nano material combining the rare earth fluoride and the oxide, and has important research significance for improving the working efficiency of the micro-nano device luminescent material in a high-temperature environment.
In summary, the existing methods for preparing heterostructures have complex synthesis processes, especially the methods for preparing rare earth oxides generally need to be carried out at high temperature, the reaction time is long, the energy conversion efficiency is low, most products have irregular shapes and poor dispersibility, and thus the application of the methods in the fields of biology, medicine and the like is greatly limited.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for quickly preparing a heterojunction micro-nano material in situ by combining rare earth fluoride-rare earth oxide on a single particle level under a mild condition, which is simple to operate.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. preparation of gold nano-islands
Evaporating a layer of gold nano film on a glass sheet cleaned in advance through a thermal evaporation coating instrument, and then annealing the gold nano film to form a gold nano island;
2. preparation of rare earth fluoride-rare earth oxide heterojunction micro-nano material
Adding the micron rod-shaped rare earth luminescent material into deionized water, performing ultrasonic homogenization at room temperature, dripping the mixture on the surface of a gold nano island, completely drying the gold nano island in an oven, and then focusing an exciting light spot at one end of a single micron rod for irradiation to convert the rare earth fluoride phase at the irradiation end into rare earth oxide, thereby obtaining the rare earth fluoride-rare earth oxide heterojunction micro-nano material.
In the step 1, the thickness of the gold nano film to be evaporated is preferably 15 to 25 nm.
In the step 1, the temperature of the annealing treatment is preferably 350-450 ℃ for 20-40 s.
In the step 2, the temperature of the oven is preferably 50-60 ℃.
In the step 2, preferably, the micron rod-shaped rare earth luminescent material is NaYF4:RE3+Micron rod-shaped crystals, RE3+Is one or two of lanthanide ions, and the rare earth fluoride-rare earth oxide heterojunction micro-nano material is NaYF4:RE3+-YOF:RE3+、NaYF4:RE3+-Y2O3:RE3+Any one of, RE3+Is any one or two of the lanthanide ions.
In the step 3, it is preferable that the excitation light has a wavelength of 520nm and an irradiation power of 20mW, or that the excitation light has a wavelength of 980nm and an irradiation power of 60 mW.
In the step 1, the irradiation time is more preferably 20 to 90 ms.
The invention has the following beneficial effects:
1. under the irradiation of laser, the noble metal nanoparticles generate local surface plasmon resonance, energy is localized near the particle surface, and the local temperature of the noble metal nanoparticles is rapidly increased and oxygen molecules adsorbed on the surface of the noble metal nanoparticles are activated along with the generation of thermal electrons along with the relaxation of the surface plasmon. Through the interaction of electrons and phonons, the heat of the noble metal nano-particles is transferred to the rare earth luminescent materials nearby. Under the double action of instant high temperature and activated oxygen, the luminescent material is instantaneously transformed into the rare earth oxide micro-nano particles. The localized temperature generated by the noble metal nanoparticles can be controlled by the illumination area and excitation light power density. Therefore, the rare earth luminescent material dispersed on the metal surface can obtain the rare earth fluoride-rare earth oxide micro-nano material with a heterostructure by controlling the illumination position and the illumination time.
2. The invention provides a preparation method of a lattice-mismatched rare earth fluoride-rare earth oxide heterojunction, which is simple and feasible, can be carried out under the condition of room temperature, and has short reaction time and small power density of required exciting light. The rare earth doped heterojunction micro-nano material generated by the reaction has regular appearance and excellent optical performance, so that the application of the rare earth doped heterojunction micro-nano material in various fields such as anti-counterfeiting, coding and decoding and the like can be greatly expanded. Due to the locality of the plasmon thermal effect, the method can realize accurate control of the in-situ reaction of the luminescent material in space, and is beneficial to the application of the method in the fields of precise electronic devices, biological markers and the like.
Drawings
FIG. 1 is a NaYF4:Eu3+SEM characterization of micron rod crystals.
FIG. 2 is a NaYF4:Eu3+XRD characterization pattern of micron rod-like crystals.
FIG. 3 is a NaYF4:Eu3+HR-TEM characterization of micron rod crystals.
FIG. 4 is a NaYF4:Eu3+Selected area electron diffraction pattern of micron rod-like crystals.
Fig. 5 is a STEM characterization graph of gold nano-islands.
FIG. 6 is a NaYF prepared in example 14:Eu3+-YOF:Eu3+SEM (scanning electron microscope) characterization graph of heterojunction micro-nano material (a is NaYF)4:Eu3+B is YOF3+)。
FIG. 7 shows fluorescence spectra measured at both ends a and b of FIG. 6.
FIG. 8 is a NaYF prepared in example 14:Eu3+-YOF:Eu3+And (3) measuring fluorescence spectra of the heterojunction micro-nano material at different positions.
FIG. 9 is a NaYF prepared in example 24:Eu3+-Y2O3:Eu3+SEM (scanning electron microscope) characterization graph of heterojunction micro-nano material (a is NaYF)4:Eu3+B is Y2O3:Eu3+)。
FIG. 10 shows fluorescence spectra measured at both ends a and b of FIG. 9.
FIG. 11 is a NaYF prepared in example 24:Eu3+-Y2O3:Eu3+And (3) measuring fluorescence spectra of the heterojunction micro-nano material at different positions.
FIG. 12 is a NaYF prepared in example 24:Eu3+-Y2O3:Eu3+And (3) an element distribution diagram of the heterojunction micro-nano material.
FIG. 13 is a NaYF prepared in example 24:Eu3+-Y2O3:Eu3+Selected electron diffraction patterns of heterojunction micro-nano materials (a corresponds to NaYF in heterostructure4:Eu3+B corresponds to Y in the heterostructure2O3:Eu3+)。
FIG. 14 is a NaYF prepared in example 24:Eu3+-Y2O3:Eu3+Heterojunction micro-nano material high-angle annular dark field scanning transmission electron microscope characterization graph (a corresponds to NaYF in heterostructure4:Eu3+B corresponds to Y in the heterostructure2O3:Eu3+)。
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples. NaYF used in the following examples4:Eu3+Micron rod-like crystal powder according to literature method "Wang, t.; siu, c.k.; yu, h.; wang, y.; li, S.; lu, w.; hao, j.; liu, h.; teng, j.h.; lei, d.y.; xu, x.; yu, S.F., infection of plasma Effect on the Upconversion emulsions of NaYF4The preparation method comprises the following steps of: firstly, mixing Y2O3And Eu2O3The powder was dissolved in dilute nitric acid and the residual nitrate was removed by heating and evaporation to form 0.2M Ln (NO)3)3(Ln ═ Y, Eu) in a transparent solution. Then 12.5mL of an aqueous solution containing 0.4g of EDTA and 1.05mL of a 5.0M aqueous NaOH solution were mixed and stirred until the solution became clear. Then, 5mL of 0.2M Ln (NO) was added to the mixture3)3(Ln＝Y,Eu)、8mL 2.0MNH4Aqueous F and 7mL of 1M dilute hydrochloric acid, stirred for 90 minutes and transferred to a Teflon-lined stainless steel autoclaveThe reaction kettle is heated to 200 ℃ and kept for 24 hours. Finally, after the reaction kettle is cooled to room temperature, precipitates are collected through centrifugation, washed for a plurality of times by deionized water and absolute ethyl alcohol and kept in a drying box at 80 ℃ for drying for 8 hours to obtain NaYF4:Eu3+Micron rod-shaped crystal powder, as shown in figures 1-4.
Example 1
1. Preparation of gold nano-islands
A layer of gold nano-film with the thickness of 20nm is evaporated on a glass sheet cleaned in advance by a thermal evaporation coating machine, and then the gold nano-film is annealed at the temperature of 400 ℃ for 30s to form a gold nano-island (see figure 5).
2.NaYF4:Eu3+-YOF:Eu3+Preparation of heterojunction micro-nano material
1g NaYF4:Eu3+Adding the micron rod-shaped crystal powder into 10mL of deionized water, performing ultrasonic treatment at room temperature for 10min, dripping the solution on the surface of the gold nano island, and then putting the gold nano island in a drying oven at the temperature of 50 ℃ until the deionized water is completely dried. Then NaYF uniformly dispersed on the surface of the gold nano island4:Eu3+Selecting a single micron rod to focus an exciting light spot at one end of the micron rod for irradiation for 20ms, wherein the wavelength of the exciting light is 532nm (coupled with the wavelength of an Au nanoparticle plasmon resonance peak), the irradiation power is 20mW, and the NaYF at the irradiation end is enabled to be4:Eu3+Phase conversion to YOF Eu3+Thereby obtaining NaYF4:Eu3+-YOF:Eu3+And (3) heterojunction micro-nano materials.
From FIG. 6, it can be seen that the morphology of the product obtained after laser irradiation does not change significantly, and the standard NaYF measured at both ends a and b in FIG. 64:Eu3+And YOF Eu3+The fluorescence spectrum of (see FIG. 7). In order to further study the luminescence characteristics of different positions on the heterojunction micron rod, the other end of the laser-treated NaYF4:Eu3+Fluorescence spectra of different positions are measured along the longitudinal direction to obtain NaYF4:Eu3+、Y5OF7:Eu3+、YOF:Eu3+The fluorescence spectrum of (see FIG. 8).
Example 2
1. Preparation of gold nano-islands
And evaporating a layer of gold nano-film with the thickness of 20nm on a glass sheet cleaned in advance through a thermal evaporation coating instrument, and then annealing the gold nano-film at 400 ℃ for 30s to form a gold nano-island.
2.NaYF4:Eu3+-Y2O3:Eu3+Preparation of heterojunction micro-nano material
1g NaYF4:Eu3+Adding the micron rod-shaped crystal powder into 10mL of deionized water, performing ultrasonic treatment at room temperature for 10min, dripping the solution on the surface of the gold nano island, and then putting the gold nano island in a drying oven at the temperature of 50 ℃ until the deionized water is completely dried. Then NaYF uniformly dispersed on the surface of the gold nano island4:Eu3+Selecting a single micron rod to focus an exciting light spot at one end of the micron rod for irradiation for 60ms, wherein the wavelength of the exciting light is 532nm (coupled with the wavelength of an Au nanoparticle plasmon resonance peak), the irradiation power is 20mW, and the NaYF at the irradiation end is enabled to be4:Eu3+Phase conversion to YOF Eu3+Thereby obtaining NaYF4:Eu3+-Y2O3:Eu3+And (3) heterojunction micro-nano materials.
From FIG. 9, it can be seen that the morphology of the product obtained after laser irradiation does not change significantly, and the standard NaYF measured at both ends a and b in FIG. 94:Eu3+And Y2O3:Eu3+The fluorescence spectrum of (see FIG. 10). In order to further study the luminescence characteristics of different positions on the heterojunction micron rod, the other end of the laser-treated NaYF4:Eu3+Fluorescence spectra of different positions are measured along the longitudinal direction to obtain NaYF4:Eu3+、Y5OF7:Eu3+、YOF:Eu3+、Y2O3:Eu3+The fluorescence spectrum of (see FIG. 11).
As can be seen from the element mapping FIG. 12, Na, Y, F, O and Eu elements can be simultaneously detected on the heterojunction nanorod, wherein the Na and F elements are only distributed at one end of the nanorod, and the O element is only distributed at the other end of the nanorod. Can be seen in the electron diffraction and high-angle annular dark-field scanning transmission electron microscope characterization chart (see FIG. 13 and FIG. 13)FIG. 14), the resulting micro-rods are made of hexagonal phase NaYF4And cubic phase Y2O3And (3) forming.
Claims (8)
1. A method for rapidly preparing a rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ is characterized by comprising the following steps:
(1) preparation of gold nano-islands
Evaporating a layer of gold nano film on a glass sheet cleaned in advance through a thermal evaporation coating instrument, and then annealing the gold nano film to form a gold nano island;
(2) preparation of rare earth fluoride-rare earth oxide heterojunction micro-nano material
Adding the micron rod-shaped rare earth luminescent material into deionized water, performing ultrasonic homogenization at room temperature, dripping the mixture on the surface of a gold nano island, completely drying the gold nano island in an oven, and then focusing an exciting light spot at one end of a single micron rod for irradiation to convert the rare earth fluoride phase at the irradiation end into rare earth oxide, thereby obtaining the rare earth fluoride-rare earth oxide heterojunction micro-nano material.
2. The method for rapidly preparing the rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ according to claim 1, is characterized in that: in the step (1), the thickness of the gold nano-film subjected to evaporation plating is 15-25 nm.
3. The method for rapidly preparing the rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ according to claim 1, is characterized in that: in the step (1), the temperature of the annealing treatment is 350-450 ℃, and the time is 20-40 s.
4. The method for rapidly preparing the rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ according to claim 1, is characterized in that: in the step (2), the temperature of the oven is 50-60 ℃.
5. The rapid in-situ preparation of rare earth fluoride-rare earth oxide heterojunction as claimed in claim 1The method for preparing the micro-nano material is characterized by comprising the following steps: in the step (2), the micron rod-shaped rare earth luminescent material is NaYF4:RE3+Micron rod-shaped crystals, RE3+Is any one or two of the lanthanide ions.
6. The method for rapidly preparing the rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ according to claim 5, is characterized in that: in the step (2), the rare earth fluoride-rare earth oxide heterojunction micro-nano material is NaYF4:RE3+-YOF:RE3+、NaYF4:RE3+-Y2O3:RE3+Any one of, RE3+Is any one or two of the lanthanide ions.
7. The method for rapidly preparing the rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ according to claim 1, is characterized in that: in the step (2), the wavelength of the excitation light is 520nm, and the irradiation power is 20mW, or the wavelength of the excitation light is 980nm, and the irradiation power is 60 mW.
8. The method for rapidly preparing the rare earth fluoride-rare earth oxide heterojunction micro-nano material in situ according to claim 1, is characterized in that: in the step (2), the irradiation time is 20-90 ms.
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| CN105523521A (en) * | 2016-01-29 | 2016-04-27 | 厦门大学 | Longitudinal coaxial heterostructure of nanowires and method for preparing longitudinal coaxial heterostructure by adopting electron beam focusing irradiation |
| CN108866625A (en) * | 2018-05-31 | 2018-11-23 | 陕西师范大学 | A kind of method of the rear-earth-doped oxide monocrystalline of original position rapid synthesis |
| CN111321373A (en) * | 2020-02-25 | 2020-06-23 | 天津大学 | Gold/silver nano-island film with multiple plasmon resonance characteristics and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105523521A (en) * | 2016-01-29 | 2016-04-27 | 厦门大学 | Longitudinal coaxial heterostructure of nanowires and method for preparing longitudinal coaxial heterostructure by adopting electron beam focusing irradiation |
| CN108866625A (en) * | 2018-05-31 | 2018-11-23 | 陕西师范大学 | A kind of method of the rear-earth-doped oxide monocrystalline of original position rapid synthesis |
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