Ultraviolet irradiation induced photochromic barium titanate fluorescent powder and application

Abstract

The application discloses a kind of ultraviolet light irradiation induced photochromic barium titanate fluorescent powder and application, including BaCO3, TiO2, Er2O3:0~2%, Yb2O3:0~2%, Nd2O3:0~2% one or more combinations;The sum of each component principle in the combination is 100%.Under the excitation of 980nm and 1550nm, the different luminescent colors exhibited by the sample, and another luminescent color exhibited under co-excitation;Based on the application of the dual-mode luminescence regulation of up-conversion luminescence based on photochromic effect, and then according to the different coloring rates before and after doping rare earth, time-based dynamic anti-counterfeiting application is carried out.In order to improve the anti-counterfeiting technical means, the application will Er 3+ ,Yb 3+ ,Nd 3+ Ion doping obtains reversible photochromic perovskite powder and its preparation method and application.Meanwhile, due to the different coloring rates of the sample before and after rare earth doping, time-based dynamic anti-counterfeiting can be realized.Expands the anti-counterfeiting and information identification means.

Description

Technical Field

[0001] This invention discloses a barium titanate phosphor induced by ultraviolet irradiation and its application, relating to the field of phosphor technology. Background Technology

[0002] Photochromic materials typically refer to compounds A that, when exposed to light of a certain wavelength, undergo a specific chemical reaction to produce product B, and then revert to their original form under light of another wavelength or thermal stimulation. Under specific wavelengths of light stimulation, not only do they change color, but their absorption and emission properties also change accordingly. Furthermore, research has shown that combining this property with luminescent materials can enable the regulation of luminescence performance. Based on material type, photochromic materials can be divided into organic and inorganic photochromic materials. Inorganic photochromic materials are significantly superior to organic photochromic materials in terms of thermal stability, reversibility, and color-changing duration, thus attracting widespread attention from researchers. Photochromic materials have potential applications in many fields, including optical anti-counterfeiting, optical information storage, and optical information encryption.

[0003] Current technologies primarily rely on static anti-counterfeiting and information encryption based on color changes. There is a lack of application of inorganic photochromic materials in dynamic, time-based anti-counterfeiting using dual-mode luminescence.

[0004] Content of this invention

[0005] The purpose of this invention is to disclose an ultraviolet irradiation-induced photochromic barium titanate phosphor and its applications. It also provides a method for preparing the phosphor and the application of inorganic photochromic materials in time-based dynamic anti-counterfeiting, thereby improving anti-counterfeiting levels and information encryption modes.

[0006] To achieve the above-mentioned technical objectives and effects, the invention is implemented through the following technical solution:

[0007] A barium titanate phosphor induced by ultraviolet irradiation photochromic, comprising one or more combinations of BaCO3, TiO2, Er2O3: 0-2%, Yb2O3: 0-2%, and Nd2O3: 0-2%;

[0008] In the combination, the sum of the principles of each component is 100%.

[0009] Furthermore, it can be used to form reversible photochromic BaTiO3 powder without rare earth doping;

[0010] The components include: BaCO3 and TiO2.

[0011] Furthermore, it can form Er 3+ ,Yb 3+ ,Nd 3+The ion-doped reversible photochromic phosphor is composed of the following raw materials in the following proportions: BaCO3, TiO2, Er2O3:0.5%, Yb2O3:0.5%, Nd2O3:0.5%.

[0012] Furthermore, it can form Er 3+ ,Yb 3+ ,Nd 3+ The ion-doped reversible photochromic phosphor is composed of the following raw materials in the following proportions: BaCO3, TiO2, Er2O3:1%, Yb2O3:1%, Nd2O3:1%.

[0013] Another objective of this invention is to disclose the preparation of a barium titanate phosphor induced by ultraviolet irradiation, comprising the following steps:

[0014] Step 1: Weigh the raw materials according to the following composition: BaCO3, TiO2, Er2O3: 0-2%, Yb2O3: 0-2%, Nd2O3: 0-2%; add alcohol and grind and mix evenly until dry;

[0015] Step 2: Place the mixed raw materials from Step 1 into a box furnace and sinter them using a high-temperature solid-state method. Remove the sample after the temperature has cooled to room temperature.

[0016] Step 3: Grind to obtain powder:

[0017] Step 4: Mix the powder and colloid evenly at a mass ratio of 1:2, then place them in an oven to dry and obtain a flexible film.

[0018] Furthermore, in step 2, the temperature of the box furnace is 1400℃, and it is kept at that temperature for 5 hours.

[0019] Another objective of this invention is to disclose an ultraviolet laser-induced color-changing phosphor used for optical anti-counterfeiting.

[0020] Furthermore, the film color change and pattern writing were induced by ultraviolet laser light, and read out under dark conditions using 980nm and 1550nm light.

[0021] Furthermore, the film is thermally bleached by heating.

[0022] Furthermore, the sample exhibited different emission colors under excitation at 980nm and 1550nm, and another emission color under co-excitation;

[0023] The application of dual-mode luminescence modulation based on upconversion luminescence of photochromic effect, and then the time-based dynamic anti-counterfeiting application based on the difference in coloring rate before and after rare earth doping.

[0024] Beneficial effects:

[0025] To improve anti-counterfeiting technology, this invention will use Er 3+ ,Yb 3+ ,Nd 3+ Ion doping yields reversible photochromic perovskite powder, along with its preparation method and applications. The photochromic powder is mixed with a colloid to form a flexible thin film. Laser irradiation colors the film, effectively writing information onto it. The original and photochromic patterns on the film exhibit different intensities of green emission when irradiated with a 980nm wavelength beam, while irradiation with 1550nm light produces strong and weak red emission. Furthermore, simultaneous excitation with 980nm and 1550nm lasers produces a different color of emission. The different coloring rates before and after rare-earth doping enable time-based dynamic anti-counterfeiting, expanding anti-counterfeiting and information identification methods.

[0026] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Attached Figure Description

[0027] Figure 1 This is a comparison image of the powder prepared in this embodiment of the invention before and after color change when saturated with a 365nm ultraviolet laser for 6 minutes.

[0028] Figure 2 These are photographs of the thin films prepared in the embodiments of the present invention.

[0029] Figure 3 This is an image of the thin film in this embodiment of the invention after being irradiated by a 365nm ultraviolet lamp, showing the optical information written on it;

[0030] Figure 4 This is an image showing the film after being heated and completely bleached, as described in an embodiment of the present invention.

[0031] Figure 5 This is a comparison of the diffuse reflectance spectra of the sample before and after color change in an embodiment of the present invention. The difference in diffuse reflectance can reach up to 27.9%.

[0032] Figure 6 This is a comparison of the photoluminescence spectra of the sample before and after color change under 980nm excitation in the embodiments of the present invention, with the highest luminescence modulation rate reaching 67.3%;

[0033] Figure 7 This is a comparison of the photoluminescence spectra of the sample before and after color change under 1550nm excitation in the embodiments of the present invention, with a luminescence modulation rate of up to 59%.

[0034] Figure 8 This is a graph showing the relationship between the color-changing film and time in an embodiment of the present invention. Detailed Implementation

[0035] To more clearly illustrate the technical solution of the present invention, the present invention will be described in detail below with reference to embodiments.

[0036] Example 1

[0037] A barium titanate phosphor induced by ultraviolet irradiation and its preparation method are as follows:

[0038] Step 1: Preparation of rare earth phosphor without doping. According to the stoichiometric ratio, 6g of BaCO3 and TiO2 are weighed into an agate mortar, and alcohol is added to grind for 30 minutes until the mixture is uniform and dry powder is obtained. The obtained powder is placed in a box furnace and sintered in air at 1400℃ for 5 hours by high-temperature solid-state method to obtain the desired powder.

[0039] Step 2: Irradiate with 5W ultraviolet light and control the irradiation time. The powder will show a gradient change in color intensity.

[0040] The phosphor prepared in Example 1 was photographed after being irradiated with ultraviolet light for 6 minutes, as shown in the image. Figure 1 As shown, the irradiated powder exhibits a distinct photochromic phenomenon. Different patterns can be displayed using a specific template.

[0041] Example 2

[0042] A barium titanate phosphor induced by ultraviolet irradiation and its preparation method are as follows:

[0043] Step 1: Design the rare earth doping ratio. Weigh 6g of BaCO3, TiO2, Er2O3:0.5%, Yb2O3:0.5%, and Nd2O3:0.5% into an agate mortar. Add alcohol and grind for 30 minutes until the mixture is uniform and a dry powder is obtained. Place the powder in a box furnace and sinter it in air at 1400℃ for 5 hours using a high-temperature solid-state method. Cool to room temperature to obtain the desired sample.

[0044] Step 2: Place the obtained sample in a ceramic mortar and grind it thoroughly to obtain a fine powder.

[0045] Step 3: Irradiate the powder with ultraviolet laser. After irradiation for 6 minutes, the powder will show obvious color change. Then, heat treatment is carried out for bleaching. Bleaching time is used to gradually fade the colored powder.

[0046] In this embodiment 2, the glass is first irradiated with ultraviolet light for 6 minutes, followed by thorough thermal bleaching through heating. Figure 4 As shown, the colored powder can be bleached, indicating that the obtained powder has good repeatability and reversibility.

[0047] Example 3

[0048] A barium titanate phosphor induced by ultraviolet irradiation and its preparation method are as follows:

[0049] Step 1: Design the rare earth doping ratio. Weigh 6g of the mixture (BaCO3, TiO2, Er2O3:1%, Yb2O3:1%, Nd2O3:1%) into an agate mortar. Add alcohol and grind for 30 minutes until uniformly mixed to obtain a dry powder. Place the powder in a box furnace and sinter it in air at 1400℃ for 5 hours using a high-temperature solid-state method. Cool to room temperature to obtain the desired sample.

[0050] Step 2: Place the obtained sample in a ceramic mortar and grind it thoroughly to obtain a fine powder.

[0051] Step 3: Irradiate the powder with ultraviolet light. After saturation irradiation for 6 minutes, use a spectrophotometer (U-4100) equipped with an integrating sphere to measure the diffuse reflectance spectrum of the powder before and after 365nm irradiation, and use a fluorescence spectrometer (F-7000) with a high-performance monochromator to measure the emission spectrum of the powder before and after 365nm irradiation.

[0052] Step 4: Mix the powder and colloid at a mass ratio of 1:2, then place them in an oven to dry, obtaining the following result. Figure 2 The flexible film shown can be printed with various patterns using a pattern template to create patterned anti-counterfeiting labels, such as... Figure 3 As shown

[0053] The powders prepared in Examples 1-3 of this invention were all sintered at a temperature of 1400℃. The color change of the flexible film after ultraviolet laser irradiation was observed, and the colored film was bleached by heating and read out using 980nm and 1550nm lasers.

[0054] By observing the different emission colors exhibited by the sample under excitation at 980nm and 1550nm, and the other emission color exhibited under co-excitation, a practical application of dual-mode luminescence modulation based on photochromic upconversion luminescence was realized. Furthermore, based on the difference in coloring rates before and after rare-earth doping, a time-based dynamic anti-counterfeiting application was simultaneously achieved.

[0055] In summary, this invention has prepared a rare-earth ion-doped photochromic phosphor. The phosphor is colored by ultraviolet light irradiation, and different optical information can be obtained by photoexcitation of different modes. Compared with traditional anti-counterfeiting phosphors, this invention can realize time-based dynamic anti-counterfeiting, expand anti-counterfeiting methods, and improve information security encryption.

[0056] The above are merely some of the embodiments of this application and are not intended to limit the application in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments shall still fall within the scope of protection of the technical solution of this application.

Claims

1. A barium titanate phosphor induced by ultraviolet irradiation to produce photochromic colors, characterized in that, Includes one or more combinations of BaCO3, TiO2, Er2O3: 0.5-2%, Yb2O3: 0.5-2%, and Nd2O3: 0.5-2%; In the combination, the total amount of each component raw material is 100%.

2. The ultraviolet irradiation-induced photochromic barium titanate phosphor according to claim 1, characterized in that: It can form Er 3+ ,Yb 3+ ,Nd 3+ The ion-doped reversible photochromic phosphor is composed of the following raw materials in the following proportions: BaCO3, TiO2, Er2O3: 0.5%, Yb2O3: 0.5%, Nd2O3: 0.5%.

3. The ultraviolet irradiation-induced photochromic barium titanate phosphor according to claim 1, characterized in that: It can form Er 3+ ,Yb 3+ ,Nd 3+ The ion-doped reversible photochromic phosphor is composed of the following raw materials in the following proportions: BaCO3, TiO2, Er2O3:1%, Yb2O3:1%, Nd2O3:1%.

4. A method for preparing a barium titanate phosphor induced by ultraviolet irradiation, characterized in that, Includes the following steps: Step 1: Weigh the raw materials according to the following components: BaCO3, TiO2, Er2O3: 0.5-2%, Yb2O3: 0.5-2%, Nd2O3: 0.5-2%; add alcohol and grind and mix evenly until dry; Step 2: Place the mixed raw materials from Step 1 into a box furnace and sinter them using a high-temperature solid-state method. Remove the sample after the temperature has cooled to room temperature. In step 2, the temperature of the box furnace is 1400℃ and it is kept at that temperature for 5 hours. Step 3: Grind to obtain powder.

5. The application of a barium titanate phosphor induced by ultraviolet irradiation as described in any one of claims 1-3 in optical anti-counterfeiting.

6. The application of the ultraviolet irradiation-induced photochromic barium titanate phosphor according to claim 5, wherein the ultraviolet irradiation-induced photochromic barium titanate phosphor and the colloid are uniformly mixed at a mass ratio of 1:2, and then placed in an oven for drying to obtain a flexible film; The film is induced to change color and pattern by ultraviolet laser light, and read out in the dark using 980nm and 1550nm light.

7. The application of the ultraviolet irradiation-induced photochromic barium titanate phosphor according to claim 6, characterized in that, The film is thermally bleached by heating.

8. The application of the ultraviolet irradiation-induced photochromic barium titanate phosphor according to claim 6, characterized in that, The sample exhibits different emission colors under excitation at 980nm and 1550nm, and another emission color under co-excitation; The application of dual-mode luminescence modulation based on upconversion luminescence of photochromic effect, and then the time-based dynamic anti-counterfeiting application based on the difference in coloring rate before and after rare earth doping.

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