Lead-free double-perovskite fluorescent powder material and preparation method and application thereof

Abstract

The invention relates to the technical field of fluorescent powder materials, in particular to a lead-free double-perovskite fluorescent powder material and a preparation method and application thereof, the chemical formula of the lead-free double-perovskite fluorescent powder material is Cs2ZrCl6: 1% of Te < 4 + > and 3% of Mo < 4 + >, and 1% of Te < 4 + > and 3% of Mo < 4 + > are doping proportions; the lead-free double-perovskite fluorescent powder material prepared by the invention can be applied to preparation of white light-near infrared LED devices and composite X-ray scintillator films; the lead-free double perovskite fluorescent powder material prepared by the invention can simultaneously realize high-efficiency white light emission, near-infrared emission and X-ray excited radiation luminescence, so that the spatial consistency and acquisition synchronism of multispectral images are ensured from a hardware source, and the problems of image pixel dislocation, resolution mismatch, high resolution ratio and the like caused by the use of various luminescent materials at present are solved. And the later image fusion processing flow is complex and time-consuming.

Description

Technical Field

[0001] This invention relates to the field of phosphor materials technology, and in particular to a lead-free double perovskite phosphor material, its preparation method and application. Background Technology

[0002] With the development of science and technology, multispectral image fusion technology has been widely applied in various fields such as medical imaging, remote sensing monitoring, food inspection, and national defense. In the field of medical imaging, by fusing X-ray, white light, and near-infrared images into a single image, a complete medical imaging atlas can be obtained. Among them, X-ray images can highlight the texture of inorganic bones, white light images can present the outline of tissues, and near-infrared images can reflect the structural features of organic tissues.

[0003] Traditional methods require the use of three different luminescent materials for white light, near-infrared, and X-ray imaging, which inevitably leads to pixel position deviations and resolution mismatches between different images. This not only requires complex visual algorithms for post-processing but also causes severe overload of computing resources. Therefore, traditional methods suffer from problems such as image pixel misalignment and resolution mismatch caused by the use of multiple luminescent materials, as well as complex and time-consuming post-processing image fusion. Summary of the Invention

[0004] The purpose of this invention is to provide a lead-free double perovskite phosphor material, its preparation method, and its application. The lead-free double perovskite phosphor material of this invention can simultaneously achieve efficient white light emission, near-infrared emission, and X-ray excited radiative emission, ensuring the spatial consistency and acquisition synchronization of multispectral images from the hardware source. It solves the problems of image pixel misalignment, resolution mismatch, and complex and time-consuming post-image fusion processing caused by the use of multiple luminescent materials.

[0005] To achieve the above objectives, in a first aspect, the present invention provides a lead-free double perovskite phosphor material, wherein the chemical formula of the lead-free double perovskite phosphor material is Cs₂ZrCl₆:1%Te 4+ 3%Mo 4+ 1%Te 4+ 3%Mo 4+ This represents the doping ratio.

[0006] The lead-free double perovskite phosphor material has a cubic crystal system and a space group of . When excited by 410nm blue light, it obtains a broad yellow light emission band with the main emission peak at 570nm-580nm.

[0007] Secondly, the present invention also provides a method for preparing a lead-free double perovskite phosphor material, comprising:

[0008] According to the chemical formula Cs₂ZrCl₆: 1%Te 4+ 3%Mo 4+ Weigh the raw materials of each element according to the proportions;

[0009] CsCl was dissolved in hydrochloric acid to obtain a clear solution.

[0010] ZrCl4 and the doped 1% TeCl4 and 3% MoCl5 were dissolved in hydrochloric acid to obtain a clear solution II.

[0011] Solution 1 and Solution 2 are mixed to produce a precipitate. The mixture is then magnetically stirred at 80°C until precipitation is complete, yielding the precipitate.

[0012] The precipitate was washed with ethanol and filtered, and then dried to obtain a coarse powder product.

[0013] The crude product is crushed and sieved to obtain lead-free double perovskite phosphor material.

[0014] The specific steps for washing and filtering the precipitate with ethanol and drying it to obtain the coarse powder product include:

[0015] The precipitate was washed three times with ethanol and filtered, then dried in an oven at 60°C for 12 hours to obtain a coarse powder product.

[0016] Thirdly, the present invention also provides an application of a lead-free double perovskite phosphor material. The lead-free double perovskite phosphor material prepared by the aforementioned method is applied to the preparation of white light-near infrared LED devices and composite X-ray scintillator films.

[0017] The white-near-infrared LED device includes a blue LED chip and a lead-free double perovskite phosphor material placed on the blue LED chip.

[0018] The specific steps for preparing the composite X-ray scintillator film include:

[0019] The lead-free double perovskite phosphor material was ground and passed through a 600-mesh sieve to obtain lead-free double perovskite phosphor material powder.

[0020] The prepolymer and curing agent were mixed in a volume ratio of 10:2 to prepare the PDMS matrix;

[0021] 0.3g of lead-free double perovskite phosphor material powder was dispersed in 1 mL of ethanol, and 2g of PDMS matrix was slowly added under ultrasonic conditions to obtain a mixture;

[0022] The mixture was stirred to form a homogeneous colloidal solution, and then vacuum degassing was performed to remove residual air and ethanol to obtain the colloidal solution.

[0023] A colloidal solution was coated onto a substrate and cured in an oven at 100°C for 5 hours to obtain a composite X-ray scintillator film.

[0024] This invention relates to a lead-free double perovskite phosphor material, its preparation method, and its application. The lead-free double perovskite phosphor material prepared by this invention can simultaneously achieve efficient white light emission, near-infrared emission, and X-ray excited radiative emission, thereby ensuring the spatial consistency and acquisition synchronization of multispectral images from the hardware source. This solves the problems of image pixel misalignment, resolution mismatch, and complex and time-consuming post-image fusion processing caused by the use of multiple luminescent materials. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0026] Figure 1 This is a flowchart of a method for preparing a lead-free double perovskite phosphor material according to the present invention.

[0027] Figure 2 This is a flowchart of the preparation of the composite X-ray scintillator film according to the present invention.

[0028] Figure 3 This is the XRD pattern of the lead-free double perovskite phosphor material of the present invention.

[0029] Figure 4 The emission spectrum of the lead-free double perovskite phosphor material of the present invention is excited at 410 nm, and the excitation spectra monitored at 575 nm and 915 nm are shown.

[0030] Figure 5 This is a schematic diagram of the color coordinates of the LED device using the lead-free double perovskite phosphor material of the present invention.

[0031] Figure 6 This is the emission spectrum of a white LED device based on lead-free double perovskite phosphor material according to the present invention.

[0032] Figure 7 The X-ray scintillation emission spectrum of the lead-free double perovskite phosphor material of this invention is shown in the schematic diagram, and compared with commercial scintillators BGO and LuAG:Ce.

[0033] Figure 8 This is the lowest detection limit for X-ray dose detection based on lead-free double perovskite phosphor material according to the present invention.

[0034] Figure 9 These are optical images of the flexible X-ray scintillator film based on lead-free double perovskite phosphor material / PDMS thin film composite material of the present invention under sunlight and 410nm excitation.

[0035] Figure 10 This is an image of a flexible X-ray scintillator film based on a lead-free double perovskite phosphor / PDMS thin film composite material, as presented in this invention. Detailed Implementation

[0036] The embodiments of the present invention are described in detail below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.

[0037] Please see Figures 1-10 In a first aspect, the present invention provides a lead-free double perovskite phosphor material, wherein the chemical formula of the lead-free double perovskite phosphor material is Cs2ZrCl6:1%Te 4+ 3%Mo 4+ 1%Te 4+ 3%Mo 4+ This represents the doping ratio.

[0038] The lead-free double perovskite phosphor material has a cubic crystal system and a space group of . When excited by 410nm blue light, it obtains a broad yellow light emission band with the main emission peak at 570nm-580nm.

[0039] The lead-free double perovskite phosphor material of the present invention, as shown by XRD diffraction pattern, has a cubic crystal system. Structure. The lead-free double perovskite phosphor material of the present invention can simultaneously achieve efficient white light emission, near-infrared emission, and X-ray excited radiative emission, thereby ensuring the spatial consistency and acquisition synchronization of multispectral images from the hardware source, solving the problems of image pixel misalignment, resolution mismatch, and complex and time-consuming post-image fusion processing caused by the use of multiple luminescent materials.

[0040] Secondly, the present invention also provides a method for preparing a lead-free double perovskite phosphor material, comprising:

[0041] S101 is formulated according to the chemical formula Cs₂ZrCl₆: 1%Te 4+ 3%Mo 4+ Weigh the raw materials of each element according to the proportions;

[0042] In this embodiment of the invention, according to the chemical formula Cs2ZrCl6:1%Te 4+ / 3%Mo 4+ Weigh out the raw materials of each element according to the proportion.

[0043] S102 dissolves CsCl in hydrochloric acid to obtain a clear solution.

[0044] In this embodiment of the invention, after weighing, CsCl is placed in beaker A and dissolved in hydrochloric acid.

[0045] S103 dissolves ZrCl4 and the doped 1% TeCl4 and 3% MoCl5 in hydrochloric acid to obtain a clear solution II;

[0046] In this embodiment of the invention, ZrCl4 and the doped 1% TeCl4 and 3% MoCl5 are placed in beaker B and dissolved in the solvent hydrochloric acid.

[0047] S104 mixes solution one and solution two to produce a precipitate. The mixture is magnetically stirred at 80°C until precipitation is complete, and the precipitate is obtained.

[0048] In this embodiment of the invention, after beakers A and B have dissolved and clarified, the solution in beaker B is directly poured into beaker A, immediately producing a precipitate. The mixture is then magnetically stirred at 80°C to ensure complete precipitation.

[0049] S105 washes the precipitate with ethanol and filters it, then dries it to obtain a coarse powder product.

[0050] The specific steps include: washing the precipitate three times with ethanol and filtering it, then drying it in a 60°C oven for 12 hours to obtain a coarse powder product.

[0051] S106 produces lead-free double perovskite phosphor material by crushing and sieving the crude product.

[0052] This invention discloses a method for preparing lead-free double perovskite phosphor materials. It employs the simplest and most direct co-precipitation synthesis method, which is easy to operate, does not involve complex processes or high-energy equipment, has high repeatability, and can be rapidly mass-produced. It avoids the drawbacks of traditional phosphor preparation methods such as high temperature and high pressure, and can emit white light without the addition of other phosphors. The lead-free double perovskite phosphor material prepared by this method can simultaneously achieve efficient white light emission, near-infrared emission, and X-ray excited radiative emission, thereby ensuring the spatial consistency and acquisition synchronization of multispectral images from the hardware source.

[0053] Secondly, the present invention also provides an application of a lead-free double perovskite phosphor material. The lead-free double perovskite phosphor material prepared by the aforementioned method is applied to the preparation of white light-near infrared LED devices and composite X-ray scintillator films.

[0054] The white-near-infrared LED device includes a blue LED chip and a lead-free double perovskite phosphor material placed on the blue LED chip.

[0055] In this embodiment of the invention, the white near-infrared LED device includes a blue light-emitting chip and a yellow lead-free double perovskite phosphor material disposed on the light-emitting chip. The phosphor can be placed directly on the light-emitting chip, or it can be mixed with a colloid such as UV adhesive or PDMS and then encapsulated on the light-emitting chip. After encapsulation, a stable light-emitting and durable white near-infrared LED device can be obtained. The yellow phosphor is the blue-excited lead-free double perovskite phosphor material of this invention. (Reference) Figure 5 ( Figure 5 (x=0.39, y=0.37) The blue LED chip of this invention can be an InGnN semiconductor LED chip with an emission wavelength of 410nm. This invention does not have a specific limitation on the amount of lead-free double perovskite phosphor material used; it can be adjusted according to actual needs. The blue LED chip is a GaN semiconductor chip, such as an InGnN semiconductor LED chip, with an emission peak wavelength of 410nm. The blue light-excited lead-free double perovskite phosphor material provided by this invention has advantages such as wide excitation range in the blue light region, high color purity, and good thermal and chemical stability, making it suitable for blue light chips and blue light-excited LED devices. The white light-near-infrared LED device provided by this invention overcomes the shortcomings of traditional commercial white light LED devices due to the lack of directly assembled yellow phosphors. The lead-free double perovskite material provided by this invention, which can be directly synthesized and excited by blue light, can simultaneously achieve efficient white light emission, near-infrared emission, and X-ray excited radiative emission, thereby ensuring spatial consistency and acquisition synchronization of multispectral images from the hardware source.

[0056] The specific steps for preparing the composite X-ray scintillator film include:

[0057] S201 grinds the lead-free double perovskite phosphor material and passes it through a 600-mesh sieve to obtain lead-free double perovskite phosphor material powder.

[0058] In this embodiment of the invention, firstly, 1%Te 4+ / 3% Mo 4+ The co-doped Cs2ZrCl6 powder was manually ground in an agate mortar and then passed through a 600-mesh sieve to ensure uniform particle size distribution.

[0059] S202 is mixed with prepolymer and curing agent in a volume ratio of 10:2 to prepare PDMS matrix;

[0060] S203 dispersed 0.3g of lead-free double perovskite phosphor material powder in 1 mL of ethanol, and slowly added 2g of PDMS matrix under ultrasonic conditions to obtain a mixture;

[0061] S204 stirs the mixture to form a homogeneous colloidal solution, and then performs vacuum degassing to remove residual air and ethanol to obtain a colloidal solution;

[0062] In this embodiment of the invention, the resulting mixture is stirred for 20 minutes to form a uniform colloidal solution, and then vacuum degassing is performed to remove residual air and ethanol.

[0063] S205 coated a colloidal solution onto a substrate and cured it in an oven at 100°C for 5 hours to obtain a composite X-ray scintillator film.

[0064] The composite X-ray scintillator film prepared by the method of the present invention can be bent and folded at will, which solves the fundamental problem of existing rigid scintillator screens. The raw materials of the present invention are abundant, the production cost is low, and the commercial use value is high. It can be applied to the fields of lighting, X-ray flat panel detectors, CT detectors, multispectral image fusion technology and other fields.

[0065] The above-disclosed embodiments are merely one or more preferred embodiments of this application and should not be construed as limiting the scope of this application. Those skilled in the art can understand that all or part of the processes for implementing the above embodiments and equivalent changes made in accordance with the claims of this application still fall within the scope of this application.

Claims

1. A lead-free double perovskite phosphor material, characterized in that, The chemical formula of the lead-free double perovskite phosphor material is Cs₂ZrCl₆:1%Te 4+ 3%Mo 4+ 1%Te 4+ 3%Mo 4+ This represents the doping ratio.

2. The lead-free double perovskite phosphor material as described in claim 1, characterized in that, The lead-free double perovskite phosphor material has a cubic crystal system and a space group of [missing information]. When excited by 410nm blue light, it obtains a broad yellow light emission band with the main emission peak at 570-580nm.

3. A method for preparing a lead-free double perovskite phosphor material, used to prepare the lead-free double perovskite phosphor material as described in any one of claims 1-2, characterized in that, include: According to the chemical formula Cs₂ZrCl₆: 1%Te 4+ 3%Mo 4+ Weigh the raw materials of each element according to the proportions; CsCl was dissolved in hydrochloric acid to obtain a clear solution. ZrCl4 and the doped 1% TeCl4 and 3% MoCl5 were dissolved in hydrochloric acid to obtain a clear solution II. Solution 1 and Solution 2 are mixed to produce a precipitate. The mixture is then magnetically stirred at 80°C until precipitation is complete, yielding the precipitate. The precipitate was washed with ethanol and filtered, and then dried to obtain a coarse powder product. The crude product is crushed and sieved to obtain lead-free double perovskite phosphor material.

4. The method for preparing lead-free double perovskite phosphor material as described in claim 3, characterized in that, The specific steps for washing the precipitate with ethanol, filtering, and drying to obtain the coarse powder product include: The precipitate was washed three times with ethanol and filtered, then dried in an oven at 60°C for 12 hours to obtain a coarse powder product.

5. An application of a lead-free double perovskite phosphor material, wherein the lead-free double perovskite phosphor material is prepared by the method described in any one of claims 3-4, characterized in that, Lead-free double perovskite phosphor materials were applied to the preparation of white light-near infrared LED devices and composite X-ray scintillator films.

6. The application of the lead-free double perovskite phosphor material as described in claim 5, characterized in that, The white light-near-infrared LED device includes a blue LED chip and a lead-free double perovskite phosphor material placed on the blue LED chip.

7. The application of the lead-free double perovskite phosphor material as described in claim 5, characterized in that, The specific steps for preparing the composite X-ray scintillator film include: The lead-free double perovskite phosphor material was ground and passed through a 600-mesh sieve to obtain lead-free double perovskite phosphor material powder. The prepolymer and curing agent were mixed in a volume ratio of 10:2 to prepare the PDMS matrix; 0.3g of lead-free double perovskite phosphor material powder was dispersed in 1 mL of ethanol, and 2g of PDMS matrix was slowly added under ultrasonic conditions to obtain a mixture; The mixture was stirred to form a homogeneous colloidal solution, and then vacuum degassing was performed to remove residual air and ethanol to obtain the colloidal solution. A colloidal solution was coated onto a substrate and cured in an oven at 100°C for 5 hours to obtain a composite X-ray scintillator film.

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