Preparation method and application of rare earth ion doped photochromic Sr10Ga6O19 fluorescent powder

Abstract

The invention relates to the technical field of photochromism, in particular to a preparation method and application of rare earth ion doped photochromic Sr10Ga6O19 fluorescent powder, and the preparation method comprises the following steps: S1, weighing SrCO3 and Ga2O3 with the purity greater than or equal to 99.9% according to a stoichiometric ratio, adding Eu2O3 as a doping source, and grinding and uniformly mixing to obtain mixed powder A; the addition amount of Eu2O3 enables the doping concentration of Eu < 3 + > to be 1 mol%; and S2, placing the mixed powder A in a muffle furnace in an air atmosphere, sintering for 6 hours at a constant temperature of 1220 DEG C, naturally cooling to room temperature along with the furnace, and grinding to obtain the Sr10Ga6O19: Eu < 3 + > ceramic powder. According to the invention, high-temperature solid-phase sintering is utilized, so that an obvious photochromic phenomenon is realized in Sr10Ga6O19.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photochromic, and particularly relates to a rare earth ion doped photochromic Sr 10 Ga6O 19 Preparation method and application of fluorescent powder. BACKGROUND

[0002] Some substances can change optical properties under the stimulation of external fields (such as light field, electric field, magnetic field, thermal field, etc.), among which the most common are photochromic, electrochromic, thermochromic, etc. Among them, because the light field control has good safety and easy operability, photochromic has attracted the attention of many people in recent years.

[0003] Photochromic mainly refers to the change of optical performance of a material under the irradiation of light of a certain specific wavelength, so that the color of the sample changes. Photochromic materials are applied in the fields of optical storage, molecular switch, anti-fake mark, etc.; in the prior art, photochromic materials are mainly divided into inorganic photochromic materials, organic photochromic materials and organic-inorganic photochromic materials; among them, inorganic photochromic materials are often used for scientific research due to their more excellent thermal stability and longer service cycle life, and the main inorganic photochromic materials at present mainly include: transition metal oxides (such as WO3, TiO2, etc.), strong oxides (BaMgSiO4, Ca2SnO2, etc.), ferroelectrics (Na 0.5 Bi 2.5 Nb2O9,Na 0.5 Bi 4.5 Ti4O 15 ,K 0.5 Na 0.5 NbO3, etc.

[0004] Inorganic photochromic is usually related to the formation of color centers induced by vacancies or the charge transfer produced by the jump of valence electrons in chromophores. The formation of color centers is closely related to the content of oxygen vacancies in the material. A larger content of oxygen vacancy defects helps to improve the photochromic performance of the material. The content of oxygen vacancies in inorganic photochromic materials can be increased by the following strategies: (1) selection of volatile elements, such as Ba 2+ 、Mg 2+ 、Ca 2+ , etc.; (2) high synthesis temperature. The higher the synthesis temperature, the more metal cations evaporate, and in order to maintain charge balance, the higher the content of oxygen vacancies in the matrix; (3) doping of low-valence elements, however, not all doping of low-valence elements can increase the oxygen vacancies. In recent years, double perovskite oxide fluorescent powder with excellent photochromic performance has shown great application prospects in the fields of optical anti-counterfeiting and information storage. However, due to the longer reaction time of double perovskite oxides to light during the color change, the efficiency in practical application is limited.

[0005] Therefore, in order to solve the above problems, the present application provides an inorganic compound Sr 10 Ga6O 19 As a photochromic matrix material, by doping Eu 3+ The preparation method of the photochromic ceramic powder which activates the matrix luminescence by ions, and the matrix color changes and erases quickly, so that the efficiency in the practical application of photochromic is improved. SUMMARY

[0006] The present application aims to provide a rare earth ion doped photochromic Sr 10 Ga6O 19 The preparation method and application of the fluorescent powder, which uses high-temperature solid-phase sintering to realize obvious photochromic phenomenon in Sr 10 Ga6O 19 .

[0007] In order to achieve the above technical purposes and achieve the above technical effects, the present application is realized by the following technical solutions:

[0008] A rare earth ion doped photochromic Sr 10 Ga6O 19 The preparation method of the fluorescent powder, comprising the following steps:

[0009] S1: weigh SrCO3 and Ga2O3 with purity ≥99.9% according to the stoichiometric ratio, and add Eu2O3 as a doping source, grind and mix to obtain mixed powder A; the addition amount of Eu2O3 is such that the doping concentration of Eu 3+ is 1 mol%;

[0010] S2: place the mixed powder A in a muffle furnace in an air atmosphere, sinter at 1220℃ for 6 hours, grind after natural cooling to room temperature in the furnace, and obtain Sr 10 Ga6O 19 :Eu 3+ ceramic powder.

[0011] On the other hand, the present application provides the Sr 10 Ga6O 19 :Eu 3+ ceramic powder prepared by the above method, which is white in original state; after irradiation with wavelength 254nm ultraviolet light for 2 minutes, the irradiated area becomes yellow; and after irradiation with wavelength 365nm ultraviolet light, it returns to the original white state.

[0012] On the other hand, the present application provides a luminescence control method of the above ceramic powder, comprising: by controlling the irradiation time of 254nm ultraviolet light, the diffuse reflection spectrum intensity of the ceramic powder in the wavelength range of 400-800nm is reduced; and the Eu3+ The intensity of light emitted when doped and activated.

[0013] On the other hand, the present invention proposes the application of the above-mentioned ceramic powder in the field of optical anti-counterfeiting, including: using a mask to cover part of the surface of the ceramic powder, and after irradiating with 254nm ultraviolet light for 2 minutes, a yellow pattern is formed in the uncovered area.

[0014] On the other hand, the present invention proposes the application of the above-mentioned ceramic powder in the field of optical information storage, including: forming yellow data points on the surface of the ceramic powder by irradiation with 254nm ultraviolet light; and erasing the yellow data points by irradiation with 365nm ultraviolet light.

[0015] The beneficial effects of this invention are:

[0016] This invention proposes a Sr 10 Ga6O 19 Eu doping 3+ A method for preparing photochromic ceramic powder, yielding photochromic Sr 10 Ga6O 19 Eu 3+ Ceramic powder; Sr of this invention 10 Ga6O 19 Eu 3+ Photochromic materials exhibit excellent photochromic properties under ultraviolet excitation; through Eu 3+ Ion doping activates its luminescence properties, while Sr 10 Ga6O 19 Eu 3+ Its rapid response speed to photochromism at 254nm facilitates the realization of the photochromic effect. It also expands the scope of exploration for inorganic photochromic materials and the application range of oxides.

[0017] This invention Sr 10 Ga6O 19 Eu 3+ Photochromic ceramic powder can rapidly change from white to yellow under 254nm ultraviolet light. This invention, Sr... 10 Ga6O 19 Eu 3+ Photochromic materials exhibit excellent photochromic properties under ultraviolet excitation, and show promising performance prospects in applications such as information storage and anti-counterfeiting labels.

[0018] In this invention, the doped ion Eu is controlled 3+The concentration of Eu2O3 in mol percent can achieve optimal adjustment of the luminescent performance of the photochromic material, and improve the luminescent performance and controllability of the photochromic effect of the material, so that better photochromic effect and performance are obtained. The traditional photochromic material has problems of photochromic stability and long required time in a long-term use process, and the present application can quickly achieve photochromic effect thereof by 254nm, and can erase the discoloration thereof by 365nm, and can be recycled multiple times. In addition, the Eu 3+ The luminescent performance after doping and activation is adjusted.

[0019] Sr 10 Ga6O 19 Doping Eu 3+ The photochromic ceramic powder has wide application potential. In the aspect of anti-counterfeiting marks, the material has obvious color change characteristics, and can be used to make anti-counterfeiting marks to improve the safety and distinguishability of products; in the field of sensors, the photochromic characteristics of the material can be used to make optical sensors to realize rapid detection and monitoring of environmental parameters; in the aspect of optical storage and display materials, the material can be used to make high-density optical storage media and high-resolution display devices to improve the storage and display effects. The material not only has high thermal stability and service life, but also can achieve obvious photochromic effect, providing a reliable basis for its popularization in various application fields.

[0020] Of course, implementing any product of the present application does not necessarily require achieving all the advantages described above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the embodiment description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0022] Figure 1 Sr 10 Ga6O 19 , Sr 10 Ga6O 19 : 1mol% Eu 3+ XRD pattern of the photochromic material;

[0023] Figure 2 Sr 10 Ga6O 19 , Sr 10 Ga6O 19 : 1mol% Eu 3+Diffuse reflectance spectra of photochromic materials before and after irradiation with a 254nm ultraviolet lamp for 2 minutes;

[0024] Figure 3 Sr as described in Example 3 10 Ga6O 19 1 mol% Eu 3+ Photochromic materials regulate their luminescence ability through photochromism.

[0025] Figure 4 Sr as described in Example 4 10 Ga6O 19 The initial color of the sample.

[0026] Figure 5 Sr as described in Example 4 10 Ga6O 19 The color of the sample after being irradiated with a 254nm ultraviolet lamp for 2 minutes. Detailed Implementation

[0027] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] As described in this embodiment, a rare earth ion-doped photochromic Sr 10 Ga6O 19 The preparation method and specific steps for phosphor luminescence modulation are as follows:

[0029] S1: Grind and mix high-purity SrCO3, Ga2O3 and Eu2O3 to obtain mixed powder A;

[0030] S2: The mixed powder A obtained in step S1 is sintered at 1220℃ in air atmosphere for 6 hours. After naturally cooling to room temperature, it is ground to obtain Sr. 10 Ga6O 19 Eu 3+ Photochromic ceramic powder;

[0031] In step S1, the raw materials SrCO3, Ga2O3, and Eu2O3 are weighed according to stoichiometric ratios, and the mixed powder A contains Eu doping ions. 3+ (Eu2O3), concentration in mol percentage, of which Eu 3+ Per 1 mol%;

[0032] The Sr prepared by this invention 10 Ga6O19 : Eu 3+ The original state is white, and when the surface is irradiated with ultraviolet light with a wavelength of 254 nm for a certain period of time, the surface area of the ceramic powder in the irradiation range will become yellow with a significant distinction.

[0033] Example 1

[0034] As Figure 1 shown

[0035] The sample obtained by the present application was subjected to X-ray diffraction analysis, and the X-ray diffraction pattern was obtained, as Figure 1 shown, from which it can be seen that Sr 10 Ga6O 19 , Sr 10 Ga6O 19 : 1mol%Eu 3+ After doping, the diffraction peaks are all matched with Sr 10 Ga6O 19 standard card PDF NO. 04-009-1734, indicating that the series of samples are all Sr 10 Ga6O 19 phase;

[0036] Pure phase means that only this compound exists in the sample, which means that the Eu 3+ ions successfully enter the Sr 10 Ga6O 19 lattice, i.e. there is no different compound or impurity with Sr 10 Ga6O 19 , so the effect of the sample obtained by the present application can accurately evaluate the characteristics and properties of Sr 10 Ga6O 19 .

[0037] Example 2

[0038] As Figure 2 shown, after 2min irradiation of 254nm lamp, Sr 10 Ga6O 19 , Sr 10 Ga6O 19 : 1mol%Eu 3+ Ceramic powder before and after discoloration diffuse reflectance spectrum.

[0039] The Sr 10 Ga6O 19 , Sr 10 Ga6O 19 : 1mol%Eu 3 +The diffuse reflection of the ceramic powder before and after discoloration.

[0040] Example 3

[0041] As Figure 3 shown, the photochromism of the sample after irradiation for different time was explored, and the Eu 3+ doping effect on the luminescence performance of the Sr 10 Ga6O 19 ceramic powder.

[0042] The Sr 10 Ga6O 19 : 1 mol% Eu 3+ ceramic powder before and after discoloration.

[0043] The sample obtained by the present application was irradiated by 254 nm ultraviolet light for 2 min, and the Sr 10 Ga6O 19 , Sr 10 Ga6O 19 : 1 mol% Eu 3+ ceramic powder before and after discoloration. Figure 2 As Figure 3 shown, the photochromism of the sample after irradiation for different time was explored, and the Eu 3+ doping effect on the luminescence performance of the Sr 10 Ga6O 19 ceramic powder.

[0044] Example 4

[0045] As Figure 4 and Figure 5 shown

[0046] By covering the mask plate, the writing of the photochromic pattern under the irradiation of 254 nm ultraviolet light can be realized.

[0047] As Figure 4 shown is the photo of the Sr 10 Ga6O 19 ceramic powder before discoloration, and the color of the ceramic powder is mainly white. By covering the mask plate, it can be obviously found that the sample changes from white to yellow under the irradiation of 254 nm ultraviolet light, as Figure 5 shown.

[0048] The Sr 10 Ga6O 19 , Sr 10 Ga6O 19 : 1 mol% Eu 3+The ceramic powder is sintered at 1220 DEG C for 6 hours to obtain an inorganic oxide material with photochromic effect, and the photochromic phenomenon has the advantages of fast response speed and high contrast. 3+ Ion-doped Ba2LaNbO6 double perovskite oxides have wide application prospects in optical switching, optical storage and optical detectors.

[0049] The preferred embodiments of the invention disclosed above are only used to illustrate the present invention. The preferred embodiments do not describe all of the details and limit the present invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the contents of the present invention. The present invention is selected and described in detail to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A rare earth ion-doped photochromic Sr 10 Ga6O 19 A method for preparing phosphors, characterized in that, Includes the following steps: S1: Weigh SrCO3 and Ga2O3 with a purity ≥99.9% according to stoichiometry, and add Eu2O3 as a dopant source. Grind and mix to obtain mixed powder A; the amount of Eu2O3 added is such that Eu... 3+ The doping concentration is 1 mol%. S2: Place the mixed powder A in a muffle furnace under air atmosphere and sinter at a constant temperature of 1220℃ for 6 hours. After naturally cooling to room temperature with the furnace, grind to obtain Sr. 10 Ga6O 19 Eu 3+ Ceramic powder.

2. A Sr prepared by the method described in claim 1 10 Ga6O 19 Eu 3+ Ceramic powder, characterized in that: The ceramic powder is originally white; after being irradiated with 254nm ultraviolet light for 2 minutes, the irradiated area turns yellow; after being irradiated with 365nm ultraviolet light, it returns to its original white state.

3. The method for controlling the luminescence of ceramic powder as described in claim 2, characterized in that: include: By controlling the irradiation time of 254nm ultraviolet light, the intensity of diffuse reflectance spectrum of ceramic powder in the wavelength range of 400-800nm ​​was reduced. Simultaneously reduce Eu 3+ The intensity of light emitted when doped and activated.

4. The application of the ceramic powder as described in claim 2 in the field of optical anti-counterfeiting, characterized in that: include: A photomask was used to cover part of the ceramic powder surface. After irradiation with 254nm ultraviolet light for 2 minutes, a yellow pattern was formed in the uncovered area.

5. The application of the ceramic powder as described in claim 2 in the field of optical information storage, characterized in that: include: Yellow data dots are formed on the surface of ceramic powder by irradiation with 254nm ultraviolet light; the yellow data dots are erased by irradiation with 365nm ultraviolet light.

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