Chlorine-doped zinc sulfide fluorescent material as well as preparation method and application thereof
By doping Cl- into a ZnS matrix, the prepared chlorine-doped zinc sulfide fluorescent material solves the problems of narrow luminescence modulation range and poor cycle stability of inorganic color-changing materials, realizing multi-mode information storage and encryption, and is suitable for optical information storage, imaging, anti-counterfeiting marking, optical or electronic fields.
Patent Information
- Application Number
- CN202511002481.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-21
- Publication Date
- 2025-10-31
AI Technical Summary
Existing inorganic color-changing materials suffer from drawbacks such as a narrow luminescence modulation range, poor cycle stability, and unclear multi-mode synergistic mechanisms, making it difficult to meet the information storage needs of the era of big data and the Internet of Things for high capacity, long-term stability, and multi-level security.
A chlorine-doped zinc sulfide fluorescent material was prepared by doping Cl- into a ZnS matrix using the molten salt shielding method. Multimode dynamic information storage was achieved through excitation with specific wavelength light and temperature treatment, using simple reaction conditions and readily available raw materials.
It achieves strong color contrast, high steady-state luminous intensity, high afterglow intensity, wide luminous modulation range, and good cycle stability, making it suitable for optical information storage, imaging, anti-counterfeiting marking, and optical or electronic fields.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of fluorescent materials technology, and particularly relates to a chlorine-doped zinc sulfide fluorescent material, its preparation method, and its application. Background Technology
[0002] In the era of big data and the Internet of Things, the explosive growth of digital information has created an urgent need for advanced storage technologies that combine large capacity, long-term stability, and multi-level security. Photochromic materials are materials whose color changes reversibly in response to external light stimulation. Based on the change in material color, its absorption spectrum and refractive index also change. Therefore, photochromic materials can be used in fields such as optical information storage, imaging, anti-counterfeiting marking, and optical / electronic devices. By integrating other optical properties with photochromic properties, it is hoped that ultra-high density, spatiotemporally adjustable, and dynamically reconfigurable multi-mode information storage and encryption can be achieved across multiple optical dimensions. Compared to traditional organic materials, inorganic photochromic materials have advantages such as good color thermal stability and fatigue resistance; however, most inorganic photochromic materials are limited to dual-mode emission and generally suffer from drawbacks such as narrow emission modulation range, poor cycle stability, and unclear multi-mode synergistic mechanisms. Summary of the Invention
[0003] In order to overcome at least one of the problems existing in the prior art, one of the objectives of the present invention is to provide a method for preparing chlorine-doped zinc sulfide fluorescent materials.
[0004] The second objective of this invention is to provide a chlorine-doped zinc sulfide fluorescent material prepared by the above-mentioned method.
[0005] The third objective of this invention is to provide a photochromic multimode fluorescent device.
[0006] The fourth objective of this invention is to provide an application of the above-mentioned chlorine-doped zinc sulfide fluorescent material or the above-mentioned photochromic multimode fluorescent device.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] The first aspect of this invention provides a method for preparing a chlorine-doped zinc sulfide fluorescent material, comprising the following steps: mixing a zinc source, a sulfur source, and a chlorine source to obtain a mixture; coating the mixture with a molten salt medium, and then performing heat treatment to obtain the chlorine-doped zinc sulfide fluorescent material; wherein the chlorine-doped zinc sulfide fluorescent material uses ZnS as a matrix and is doped with Cl. - The Cl - The doping molar concentration is greater than 0 and less than 100%.
[0009] Compared to traditional high-temperature solid-state methods, this invention employs a specific molten salt shielding method, which can achieve Cl -The chlorine-doped zinc sulfide phosphor prepared by specific doping in a ZnS matrix exhibits strong color-changing contrast, high steady-state luminescence intensity, high afterglow intensity, wide luminescence modulation range, and good cycle stability. Furthermore, the preparation method provided by this invention requires no expensive equipment or complex process control, uses simple reaction conditions, readily available raw materials, has low production costs, and is easily suitable for industrial production.
[0010] Preferably, the Cl - The doping molar concentration is 2 to 30%; for example, it can be any value of 2%, 5%, 10%, 15%, 20%, 25% or 30% or any range between two.
[0011] By analyzing Cl - Optimizing the doping molar concentration can achieve better luminescence performance.
[0012] Preferably, the zinc source includes zinc sulfide, zinc oxide, or a combination thereof; more preferably, the zinc source is selected from zinc sulfide (ZnS).
[0013] Preferably, the sulfur source includes zinc sulfide, elemental sulfur, or a combination thereof; more preferably, the sulfur source is selected from zinc sulfide (ZnS).
[0014] Preferably, the chlorine source includes at least one of sodium chloride, potassium chloride, calcium chloride, or lithium chloride; more preferably, the chlorine source is selected from sodium chloride (NaCl).
[0015] Preferably, the temperature of the heat treatment is 1000℃ to 1300℃; for example, it can be any value or a range between 1000℃, 1050℃, 1100℃, 1150℃, 1200℃, 1250℃ or 1300℃.
[0016] Preferably, the heat treatment time is 0.5h to 30h; for example, it can be any value or a range between 0.5h, 1h, 5h, 10h, 15h, 20h, 25h or 30h.
[0017] Preferably, the molten salt medium includes sodium chloride, potassium chloride, or a combination thereof; more preferably, the molten salt medium is selected from sodium chloride (NaCl).
[0018] Preferably, the chlorine-doped zinc sulfide fluorescent material appears dark gray under light excitation at wavelengths of 265nm-305nm, and appears white after heat treatment at a temperature >200℃; more preferably, the chlorine-doped zinc sulfide fluorescent material appears dark gray under light excitation at a wavelength of 305nm, and appears white after heat treatment at a temperature of 375℃.
[0019] Preferably, the chlorine-doped zinc sulfide fluorescent material exhibits a continuous and repeating color change of dark gray and white under alternating excitation with light at a wavelength of 265nm-305nm and heating treatment at a temperature >200℃; more preferably, the chlorine-doped zinc sulfide fluorescent material exhibits a continuous and repeating color change of dark gray and white under alternating excitation with light at a wavelength of 305nm and heating treatment at a temperature of 375℃.
[0020] Preferably, the chlorine-doped zinc sulfide fluorescent material produces blue-green steady-state luminescence under light excitation at wavelengths of 330nm-360nm and green afterglow luminescence under light excitation at wavelengths of 360nm-400nm; more preferably, the chlorine-doped zinc sulfide fluorescent material produces blue-green steady-state luminescence under light excitation at wavelengths of 330nm and green afterglow luminescence under light excitation at wavelengths of 390nm.
[0021] A second aspect of the present invention provides a chlorine-doped zinc sulfide fluorescent material prepared by the preparation method described in the first aspect of the present invention.
[0022] A third aspect of the present invention provides a photochromic multimode fluorescent device comprising the chlorine-doped zinc sulfide fluorescent material described in the second aspect of the present invention.
[0023] Preferably, the photochromic multimode fluorescent device appears dark gray under light excitation at wavelengths of 265nm-305nm, and appears white after heat treatment at a temperature >200℃; more preferably, the photochromic multimode fluorescent device appears dark gray under light excitation at a wavelength of 305nm, and appears white after heat treatment at a temperature of 375℃.
[0024] Preferably, the photochromic multimode fluorescent device exhibits a continuous and repeating color change between dark gray and white when subjected to alternating excitation with light at wavelengths of 265nm-305nm and heating treatment at a temperature >200℃; more preferably, the photochromic multimode fluorescent device exhibits a continuous and repeating color change between dark gray and white when subjected to alternating excitation with light at wavelengths of 305nm and heating treatment at a temperature of 375℃.
[0025] Preferably, the photochromic multimode fluorescent device produces steady-state blue-green emission under excitation with light at wavelengths of 330nm-360nm and green afterglow emission under excitation with light at wavelengths of 360nm-400nm; more preferably, the photochromic multimode fluorescent device produces steady-state blue-green emission under excitation with light at wavelengths of 330nm and green afterglow emission under excitation with light at wavelengths of 390nm.
[0026] The photochromic multimode fluorescent device prepared using the chlorine-doped zinc sulfide fluorescent material provided by this invention can realize multimode dynamic information storage and utilization, and has the advantages of wide emission modulation range, good cycle stability and clear multimode synergistic mechanism.
[0027] The fourth aspect of the present invention provides an application of a chlorine-doped zinc sulfide fluorescent material as described in the second aspect of the present invention, or a photochromic multimode fluorescent device as described in the third aspect of the present invention, in the fields of optical information storage, imaging, anti-counterfeiting marking, optics, or electronics.
[0028] The chlorine-doped zinc sulfide fluorescent material and photochromic multimode fluorescent device provided by this invention have continuous and repeatable color changes. Under specific wavelength light excitation and specific temperature heating treatment, they can display dark gray and white respectively, and can achieve continuous and repeatable color changes between dark gray and white. This continuous and repeatable color change and fading characteristic makes the material and device have good reversibility and cyclicity, and can be used in optical information storage, imaging, anti-counterfeiting marking, optics or electronics and other fields.
[0029] The chlorine-doped zinc sulfide fluorescent material and photochromic multimode fluorescent device provided by this invention can realize luminescence regulation and information storage. Under the excitation of specific wavelength light, it can produce blue-green steady-state luminescence and green afterglow luminescence. Moreover, through the color-changing characteristics, its luminescence can be statically and dynamically regulated respectively. This luminescence regulation characteristic makes the material and the device applicable to optical information storage, imaging, anti-counterfeiting marking, optics or electronics and other fields.
[0030] The chlorine-doped zinc sulfide fluorescent material and photochromic multimode fluorescent device provided by this invention can achieve information security protection. Because the aforementioned material and device possess static and dynamic emission control capabilities, this characteristic can be utilized to protect information. For example, under specific excitation conditions, the emission color of the photochromic multimode phosphor can be changed, thereby achieving dynamic information encryption or identification and increasing information storage security.
[0031] The chlorine-doped zinc sulfide fluorescent material and photochromic multimode fluorescent device provided by this invention have good durability and stability, and can therefore adapt to various environmental conditions, which is crucial for long-term information storage requirements.
[0032] The beneficial effects of this invention are: this invention employs a specific molten salt shielding method, which can achieve Cl - The chlorine-doped zinc sulfide fluorescent material prepared by specific doping in the ZnS matrix has the characteristics of strong color contrast, high steady-state luminescence intensity, high afterglow intensity, wide luminescence modulation range and good cycle stability. The material prepared by this method can be used to prepare photochromic multimode fluorescent devices to realize multimode information storage and encryption. Attached Figure Description
[0033] Figure 1 The X-ray powder diffraction patterns of the samples in Examples 1-5 are shown.
[0034] Figure 2 This is a comparison of the diffuse reflectance spectra of the sample before and after irradiation at 305 nm with a photograph of the sample.
[0035] Figure 3 The image shows a comparison of the diffuse reflectance spectra of the sample before and after irradiation at 305 nm, and a comparison of the sample photograph.
[0036] Figure 4 This is a comparison of the diffuse reflectance spectra of the sample before and after 305nm irradiation in Example 3, and a comparison of the sample photograph.
[0037] Figure 5 The image shows the changes in diffuse reflectance spectra of the sample in Example 3 before and after irradiation at 305 nm and after heating at different temperatures after irradiation.
[0038] Figure 6 The fluorescence emission spectrum of the sample in Comparative Example 1 under 330 nm excitation is shown.
[0039] Figure 7 The fluorescence emission spectra of the sample in Example 3 under excitation at 330 nm and fluorescence excitation spectra under emission at 460 nm and 520 nm are shown.
[0040] Figure 8 The image shows a comparison of the fluorescence emission spectra of the sample from Example 3 and the sample from Comparative Example 2 under 330 nm excitation.
[0041] Figure 9 This is a comparison of the afterglow decay curves of the sample in Example 3 and the sample in Comparative Example 2 under 390nm excitation.
[0042] Figure 10 The image shows the long-term afterglow decay curve of the sample in Example 3 under 390nm excitation.
[0043] Figure 11 The afterglow spectra of the sample in Example 3 at different times under 390 nm excitation.
[0044] Figure 12 This is a comparison of steady-state emission photographs and afterglow variation photographs of the sample in Example 3 after being irradiated with 305nm light for different times and then excited with 365nm light. Detailed Implementation
[0045] The following specific embodiments further illustrate the content of the present invention in detail. It should also be understood that the following embodiments are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the principles described herein are all within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make selections within a suitable range based on the description herein, and are not intended to be limited to the specific data in the examples below. Unless otherwise specified, the raw materials, reagents, or apparatus used in the following embodiments and comparative examples can be obtained from conventional commercial sources or by existing known methods.
[0046] Example 1
[0047] A chlorine-doped zinc sulfide fluorescent material with the chemical formula: ZnS:Cl, wherein Cl... - The doping molar concentration was 2%, and it was prepared using the molten salt shielding method. The specific preparation steps are as follows:
[0048] (1) Based on the above design of the composition of the photochromic multimode phosphor, the matrix is ZnS, and the dopant ion is Cl. - The doping amount is 2 mol%. Zinc sulfide (ZnS) and sodium chloride (NaCl) are weighed according to the stoichiometric ratio of the chemical formula. Then, each raw material is placed in an agate mortar and ground for 5 minutes (the grinding medium is anhydrous ethanol, and the mass-volume ratio of the material to anhydrous ethanol is 1 g: 3 mL) to make the raw materials fully and evenly mixed to obtain a mixture.
[0049] (2) Transfer the mixture obtained in step (1) to a corundum crucible and coat the mixture with molten salt (sodium salt NaCl), cover it and place it in a high-temperature reaction furnace for calcination at 1000°C for 0.5h; cool naturally to room temperature, take out the sample, dissolve and remove the molten salt coating on the surface with deionized water to obtain the sample in this example, which is a multimode phosphor.
[0050] Example 2
[0051] A chlorine-doped zinc sulfide fluorescent material with the chemical formula: ZnS:Cl, wherein Cl... - The doping molar concentration was 10%, and it was prepared using the molten salt shielding method. The specific preparation steps are as follows:
[0052] (1) Based on the above design of the composition of the photochromic multimode phosphor, the matrix is ZnS, and the dopant ion is Cl. -The doping amount is 10 mol%. Zinc sulfide (ZnS) and sodium chloride (NaCl) are weighed according to the stoichiometric ratio of the chemical formula. Then, each raw material is placed in an agate mortar and ground for 5 minutes (the grinding medium is anhydrous ethanol, and the mass-volume ratio of the material to anhydrous ethanol is 1 g: 3 mL) to make the raw materials fully and evenly mixed to obtain a mixture.
[0053] (2) Transfer the mixture obtained in step (1) into a corundum crucible, and coat the mixture with molten salt (sodium salt NaCl), cover it and place it in a high-temperature reaction furnace for calcination at 1050°C for 5 hours; cool naturally to room temperature, take out the sample, and dissolve and remove the molten salt coating on the surface with deionized water to obtain the sample in this example, which is a multimode phosphor.
[0054] Example 3
[0055] A chlorine-doped zinc sulfide fluorescent material with the chemical formula: ZnS:Cl, wherein Cl... - The doping molar concentration was 20%, and it was prepared using the molten salt shielding method. The specific preparation steps are as follows:
[0056] (1) Based on the above design of the composition of the photochromic multimode phosphor, the matrix is ZnS, and the dopant ion is Cl. - The doping amount is 20 mol%. Zinc sulfide (ZnS) and sodium chloride (NaCl) are weighed according to the stoichiometric ratio of the chemical formula. Then, each raw material is placed in an agate mortar and ground for 5 minutes (the grinding medium is anhydrous ethanol, and the mass-volume ratio of the material to anhydrous ethanol is 1 g: 3 mL) to make the raw materials fully and evenly mixed to obtain a mixture.
[0057] (2) Transfer the mixture obtained in step (1) to a corundum crucible and coat the mixture with molten salt (sodium salt NaCl), cover it and place it in a high-temperature reaction furnace for calcination at 1100°C for 15 hours; cool naturally to room temperature, take out the sample, dissolve and remove the molten salt coating on the surface with deionized water to obtain the sample in this example, which is a multimode phosphor.
[0058] Example 4
[0059] A chlorine-doped zinc sulfide fluorescent material with the chemical formula: ZnS:Cl, wherein Cl... - The doping molar concentration was 25%, and it was prepared using the molten salt shielding method. The specific preparation steps are as follows:
[0060] (1) Based on the above design of the composition of the photochromic multimode phosphor, the matrix is ZnS, and the dopant ion is Cl. -The doping amount is 25 mol%. Zinc sulfide (ZnS) and sodium chloride (NaCl) are weighed according to the stoichiometric ratio of the chemical formula. Then, each raw material is placed in an agate mortar and ground for 5 minutes (the grinding medium is anhydrous ethanol, and the mass-volume ratio of the material to anhydrous ethanol is 1 g: 3 mL) to make the raw materials fully and evenly mixed to obtain a mixture.
[0061] (2) Transfer the mixture obtained in step (1) into a corundum crucible, and coat the mixture with molten salt (sodium salt NaCl), cover it and place it in a high-temperature reaction furnace for calcination at 1200°C for 20 hours; cool naturally to room temperature, take out the sample, and dissolve and remove the molten salt coating on the surface with deionized water to obtain the sample in this example, which is a multimode phosphor.
[0062] Example 5
[0063] A chlorine-doped zinc sulfide fluorescent material with the chemical formula: ZnS:Cl, wherein Cl... - The doping molar concentration was 30%, and it was prepared using the molten salt shielding method. The specific preparation steps are as follows:
[0064] (1) Based on the above design of the composition of the photochromic multimode phosphor, the matrix is ZnS, and the dopant ion is Cl. - The doping amount is 30 mol%. Zinc sulfide (ZnS) and sodium chloride (NaCl) are weighed according to the stoichiometric ratio of the chemical formula. Then, each raw material is placed in an agate mortar and ground for 5 minutes (the grinding medium is anhydrous ethanol, and the mass-volume ratio of the material to anhydrous ethanol is 1 g: 3 mL) to make the raw materials fully and evenly mixed to obtain a mixture.
[0065] (2) The mixture obtained in step (1) is transferred to a corundum crucible and coated with molten salt (sodium salt NaCl). The mixture is then covered and placed in a high-temperature reaction furnace and calcined at 1300°C for 30 hours. After naturally cooling to room temperature, the sample is taken out and the molten salt coating on the surface is removed by dissolving it with deionized water. This yields the sample in this example, which is a multimode phosphor.
[0066] Comparative Example 1
[0067] This comparative example provides undoped Cl. - The zinc sulfide sample has the chemical formula ZnS.
[0068] Comparative Example 2
[0069] A chlorine-doped zinc sulfide fluorescent material with the chemical formula: ZnS 0.8 Cl 0.2 That is, ZnS 0.8 0.2Cl was prepared using a traditional high-temperature solid-state method. The specific preparation steps are as follows:
[0070] (1) Based on the above design of the composition of the photochromic multimode phosphor, the matrix is ZnS, and the dopant ion is Cl. - The doping amount is 20 mol%. Zinc sulfide (ZnS) and sodium chloride (NaCl) are weighed according to the stoichiometric ratio of the chemical formula. Then, each raw material is placed in an agate mortar and ground for 5 minutes (the grinding medium is anhydrous ethanol, and the mass-volume ratio of the material to anhydrous ethanol is 1 g: 3 mL) to make the raw materials fully and evenly mixed to obtain a mixture.
[0071] (2) Transfer the mixture obtained in step (1) into a corundum crucible, cover it and place it in a high-temperature reaction furnace and calcine it at 1300℃ for 5 hours under a nitrogen atmosphere; cool it naturally to room temperature, take out the sample and grind it for 30 minutes to obtain the sample in this example, which is a multimode phosphor.
[0072] Performance testing
[0073] 1. Component analysis
[0074] The samples prepared in Examples 1-5 were subjected to XRD tests using an X-ray diffractometer (model D / MAX 2200VPC) from Rigaku Corporation, Japan. Figure 1 The X-ray powder diffraction patterns are those of samples from Examples 1-5. Figure 1 It can be seen that the X-ray powder diffraction patterns of the chlorine-doped zinc sulfide fluorescent materials prepared in Examples 1-5 are consistent with the ICSD ZnS standard card (PDF 36-1450), indicating that no other phases or impurities were introduced.
[0075] 2. Reflectivity
[0076] Figure 2 Comparison of diffuse reflectance spectra of sample 1 before and after irradiation at 305 nm with sample photographs; Figure 3 Comparison of diffuse reflectance spectra of sample 2 before and after irradiation at 305 nm with sample photographs; Figure 4 This is a comparison of the diffuse reflectance spectra of the sample in Example 3 before and after 305nm irradiation, and a comparison of the sample photograph. Figures 2-4 It can be seen that the reflectance of the ZnS raw material in Comparative Example 1 remained basically unchanged before and after irradiation, indicating that it did not have a color-changing effect; while compared with the sample prepared by the traditional high-temperature solid-state method in Comparative Example 2, the chlorine-doped zinc sulfide fluorescent material prepared by the molten salt shielding method in Example 1 showed significantly enhanced absorption in the visible light range and maintained a low reflectance in the near-infrared light range. The chlorine doping method using a specific method... - The sample obtained in Example 3 exhibited a more significant color-changing effect.
[0077] 3. Reversibility and recoverability
[0078] Figure 5This image shows the changes in diffuse reflectance spectra of the sample from Example 3 before and after 305 nm irradiation, and after heating at different temperatures following irradiation. Figure 5 It can be seen that the sample of Example 3 can be restored to the bleached state after being heated at 375°C after irradiation, which is basically the same as the state before irradiation. It can be seen that heating at 375°C can effectively remove the discoloration effect, and heating at other temperatures can also remove the discoloration effect to a certain extent, indicating that the sample of Example 3 has good reversibility and recoverability.
[0079] 4. Excitation and emission spectral intensities
[0080] The fluorescence emission and excitation spectra of each sample were measured using an Edinburgh FLS1000 steady-state transient fluorescence spectrometer with a 500W xenon lamp as the excitation source. Figure 6 The fluorescence emission spectrum of Comparative Example 1 sample under 330 nm excitation; Figure 7 The fluorescence emission spectra of the sample in Example 3 under excitation at 330 nm and fluorescence excitation spectra under emission at 460 nm and 520 nm are shown. Figure 8 This is a comparison of the fluorescence emission spectra of the sample from Example 3 and the sample from Comparative Example 2 under 330 nm excitation. Figures 6-8 It can be seen that the sample of Example 3 has good luminescence performance, and compared with the sample of Comparative Example 2, the sample of Example 3 has a stronger steady-state luminescence intensity.
[0081] 5. Afterglow intensity
[0082] Figure 9 A comparison of the afterglow decay curves of the sample in Example 3 and the sample in Comparative Example 2 under 390nm excitation; Figure 10 The image shows the long-term afterglow decay curve of the sample in Example 3 under 390nm excitation. Figure 11 The images show the afterglow spectra of the sample from Example 3 at different times under 390 nm excitation. Figures 9-11 It can be seen that the sample of Example 3 has a long-lasting and high-intensity green afterglow, and compared with the sample of Comparative Example 2, the sample of Example 3 has a higher afterglow intensity.
[0083] 6. Luminous modulation
[0084] Figure 12 This is a comparison of steady-state emission photographs and afterglow variation photographs of the sample from Example 3 after being irradiated at 305 nm for different times and then excited by 365 nm light. Figure 12 As can be seen, the steady-state and afterglow luminescence of the sample in Example 3 can be statically and dynamically controlled by 305nm irradiation, and the modulation amplitude is large, which solves the problem of narrow luminescence modulation range of inorganic color-changing materials.
[0085] As can be seen from the above, compared with the traditional high-temperature solid-state method, the molten salt shielding method used in this embodiment of the invention produces samples with stronger color-changing contrast, steady-state luminescence intensity, and stronger afterglow. The chlorine-doped zinc sulfide phosphor prepared in this embodiment of the invention appears dark gray under light excitation at wavelengths of 265nm-305nm, and white after heating at temperatures >200℃; under alternating light excitation at 265nm-305nm and heating at temperatures >200℃, it exhibits a continuous and repetitive color change between dark gray and white; under light excitation at wavelengths of 330nm-360nm, it produces steady-state blue-green luminescence, and under light excitation at wavelengths of 360nm-400nm, it produces green afterglow luminescence. Furthermore, its luminescence can be statically and dynamically controlled through its color-changing properties, which is beneficial for multi-mode dynamic information storage. This material can solve the problems of narrow luminescence modulation range, poor cycle stability, and unclear multi-mode synergistic mechanisms existing in traditional organic or inorganic color-changing materials. Therefore, the photochromic multi-mode phosphor prepared in this invention has broad application prospects in the field of inorganic luminescent material information storage.
[0086] In summary, this invention employs a specific molten salt shielding method to achieve Cl - The chlorine-doped zinc sulfide fluorescent material prepared by specific doping in the ZnS matrix has the characteristics of strong color contrast, high steady-state luminescence intensity, high afterglow intensity, wide luminescence modulation range and good cycle stability. The material prepared by this method can be used to prepare photochromic multimode fluorescent devices to realize multimode information storage and encryption.
Claims
1. A method for preparing a chlorine-doped zinc sulfide fluorescent material, characterized in that, Includes the following steps: A zinc source, a sulfur source, and a chlorine source are mixed to obtain a mixture; the mixture is then coated with a molten salt medium and subjected to heat treatment to obtain the chlorine-doped zinc sulfide fluorescent material; the chlorine-doped zinc sulfide fluorescent material uses ZnS as a matrix and is doped with Cl. - The Cl - The doping molar concentration is greater than 0 and less than 100%.
2. The preparation method according to claim 1, characterized in that, The Cl - The molar concentration of the doping is 2-30%.
3. The preparation method according to claim 1, characterized in that, The zinc source includes zinc sulfide, zinc oxide, or a combination thereof; And / or, the sulfur source includes zinc sulfide, elemental sulfur, or a combination thereof; And / or, the chlorine source includes at least one of sodium chloride, potassium chloride, calcium chloride, or lithium chloride.
4. The preparation method according to claim 1, characterized in that, The heat treatment temperature is 1000℃~1300℃.
5. The preparation method according to claim 1, characterized in that, The heat treatment time is 0.5h to 30h.
6. The preparation method according to claim 1, characterized in that, The molten salt medium includes sodium chloride, potassium chloride, or a combination thereof.
7. The preparation method according to claim 1, characterized in that, The chlorine-doped zinc sulfide fluorescent material appears dark gray under light excitation at wavelengths of 265nm-305nm, and turns white after heat treatment at temperatures >200℃. And / or, the chlorine-doped zinc sulfide fluorescent material exhibits a continuous and repeating color change of dark gray and white under alternating excitation with light at wavelengths of 265nm-305nm and heating treatment at temperatures >200℃; And / or, the chlorine-doped zinc sulfide fluorescent material produces blue-green steady-state luminescence under light excitation at wavelengths of 330nm-360nm, and green afterglow luminescence under light excitation at wavelengths of 360nm-400nm.
8. A chlorine-doped zinc sulfide fluorescent material prepared by any one of claims 1 to 7.
9. A photochromic multimode fluorescent device, characterized in that, Includes the chlorine-doped zinc sulfide fluorescent material as described in claim 8.
10. The application of a chlorine-doped zinc sulfide fluorescent material as described in claim 8, or a photochromic multimode fluorescent device as described in claim 9, in optical information storage, imaging, anti-counterfeiting marking, optics, or electronics.