Stimulus-responsive single-doped UVC-red light dual-band emission material and preparation method and application thereof

Abstract

The invention provides a stimuli-responsive single-doped UVC-red light dual-band emission inorganic rare earth luminescent material as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing Na2CO3, Sr2CO3, SiO2 and Pr2O3 in proportion to obtain raw material mixed powder; (2) calcining the raw material mixed powder in calcining equipment to obtain a calcined product; and (3) grinding the calcined product to obtain the material Na2Sr1-xBaxSi2O6: y% Pr < 3 + >, x = 0-0.35, and y = 0.25-2, in addition, the stimuli-responsive single-doped UVC-red light dual-band emission material can also be applied to bright and dark field imaging. According to the invention, only a single light-emitting center is doped in a proper single matrix, so that on one hand, possible negative effects of a plurality of doped centers on the matrix are reduced, the properties of the material are more stable and excellent, on the other hand, raw materials and steps required by material preparation are simplified, and the requirements of industrial large-scale production are met.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic luminescent materials, and in particular to a stimulus-responsive single-doped UVC-red light dual-band emitting material and a preparation method and application thereof. Background Art

[0002] The rapid development of the information age has put forward higher requirements for functional materials as the cornerstone of information technology. Realizing the transition from single function to multifunctional coupling has become one of the main directions of the development of modern high-tech materials. Most of the reported rare earth-based luminescent materials are limited to single-mode optical response or light output, which is not conducive to exploring new application directions. Multimodal luminescent materials can achieve multiple optical responses and emission modes, and are expected to become a good way for multifunctional applications.

[0003] At present, the emission region of multimodal luminescent materials is limited to the visible light and infrared light bands, which means that the emission signal must be observed in a dark environment to avoid strong interference from ambient light. At the same time, the increase in multifunctionality often requires the use of a co-doping strategy to introduce more luminescent ions, which increases the cost and complexity of material design and synthesis. Therefore, for single-doped phosphors, it is still a challenge to simultaneously achieve multimodal luminescence characteristics in bright field and dark field. Summary of the invention

[0004] The present invention provides a stimulus responsive single-doped UVC-red light dual-band emitting material and a preparation method and application thereof, in order to solve the above-mentioned problems.

[0005] The present invention provides a stimulus responsive single-doped UVC-red light dual-band emission material, the chemical structure of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0~0.35, y=0.25~2.

[0006] A method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material according to the solution of the present invention comprises the following steps:

[0007] Step (i), preparing raw materials, the raw materials include Na2CO3, Sr2CO3, SiO2 and Pr2O3, mixing Na2CO3, Sr2CO3, SiO2 and Pr2O3 according to a proportion, putting them into a mortar, pouring alcohol into the mortar, and then grinding and mixing the raw materials to obtain a raw material mixed powder;

[0008] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 800-1200° C., the calcination time is 2-4 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0009] Step (iii), putting the calcined product into a mortar for grinding, grinding the calcined product to 150-250 μm, and obtaining the stimulus responsive single-doped UVC-red light dual-band emitting material.

[0010] As a further preference of the above scheme:

[0011] In the step (i), Na2CO3, Sr2CO3 and SiO2 are mixed in a molar ratio of 1:1:2.

[0012] As a further preference of the above scheme:

[0013] In the step (i), the proportion of Pr2O3 is 0.25% to 2% of the total molar ratio of the raw material mixed powder.

[0014] As a further preference of the above scheme:

[0015] The raw materials in step (a) also include Ba2CO3, and Na2CO3, Ba2CO3, Sr2CO3, SiO2 and Pr2O3 are mixed in proportion, wherein Na2CO3, Ba2CO3, Sr2CO3, SiO2 are mixed in a molar ratio of 1:x:1-x:2, and the proportion of Pr2O3 accounts for 0.25% to 2% of the total molar ratio of the raw material mixed powder.

[0016] As a further preference of the above scheme:

[0017] The proportion of Pr2O3 is 1.5% of the total molar ratio of the raw material mixed powder.

[0018] The present invention provides an application of a stimulus-responsive single-doped UVC-red light dual-band emitting material, and applies the material to bright-field and dark-field imaging.

[0019] The beneficial effects of the present invention are as follows:

[0020] 1. The stimulus responsive single-doped UVC-red light dual-band emitting material of the present invention is Pr 3+ Single ion-doped materials only dope a single luminescent center in a suitable single matrix. On the one hand, this reduces the negative impact of multiple doping centers on the matrix itself, making the material properties more stable and excellent. On the other hand, it simplifies the raw materials and steps required for material preparation, meeting the needs of industrial large-scale production.

[0021] 2. The luminescent material obtained by the preparation method of the present invention can emit light in two bands, UVC and red light, under an X-ray excitation source, and is an extremely rare UVC-red dual-emission material. In addition, this material also integrates the special properties of long afterglow and photochromism of UVC / red light, making it a multimodal luminescent material that meets the requirements of the development of modern high-tech materials. This material provides a new approach for multifunctional optical storage and bright and dark field imaging applications;

[0022] 3. Currently, UVC materials are very scarce, and due to the huge energy level difference between UVC and red light emission, in order to achieve the luminescence of both at the same time, people tend to use high-energy excitation sources such as X-rays. The present invention pioneered the use of materials that can emit UVC and red light under ultraviolet light excitation. In the present invention, a common ultraviolet light source of 254nm can simultaneously excite UVC and red light emission, which greatly reduces the difficulty and cost of obtaining the excitation source required for the material; in addition, the present invention uses Na2CO3, Sr2CO3, SiO2 and Pr2O3 as raw materials to prepare stimulus-responsive single-doped UVC-red light dual-band emission materials, and the raw materials are widely available and low in cost; the operating environment is mild, no special gas atmosphere is required, the operation is simple, and it is suitable for large-scale industrial production; the stimulus-responsive single-doped UVC-red light dual-band emission material prepared using the raw materials of the aforementioned ratio has better luminescence intensity, can effectively dope the emission center, has high luminescence intensity, and has a wide range of color change; and enables the material to emit light of different wavelengths at different temperatures and maintain luminescence intensity; no harmful substances are produced during the preparation process;

[0023] 4. The stimulus-responsive single-doped UVC-red light dual-band emission material of the present invention can emit red light normally in a dark field, and in a bright field, due to the blocking of UVC by the atmosphere, the UVC emitted by the material can be collected and monitored with "zero noise", which solves the current problem of imaging of inorganic rare earth luminescent materials under sunlight and further expands its application in anti-counterfeiting.

[0024] 5. The stimulus responsive single-doped UVC-red light dual-band emitting material of the present invention has a chemical expression of: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , specifically:

[0025] (1) Na2SrSi2O6 is used as the matrix. The reason is that Na2SrSi2O6 is prepared by using Na2CO3, Sr2CO3 and SiO2. The matrix is ​​a cyclic silicate with a unit cell parameter of and It consists of a folded six-membered ring [Si6O 18 ] 12-In this matrix, six to nine oxygen ligands are used to coordinate alkali metal atoms and alkaline earth metal atoms. When such a matrix is ​​doped with rare earth elements, the oxygen vacancies in the crystal structure and the Ca 2+ Cation vacancies will produce intrinsic defects, making the structure of this matrix more susceptible to forming new crystal structures with rare earth elements than other matrices;

[0026] (2) Furthermore, the present invention designs to dope the rare earth element Pr in the Na2SrSi2O6 matrix. 3+ , because Pr 3+ It has a very special 5d energy level among rare earth ions, which enables it to meet the large Stokes shift required for UVC emission when used as a luminescence center. 3+ Also has 3 P0 to 1 The red 4f-4f transition of D2, and most of the undesirable emission in this transition will be quenched at room temperature, Pr 3+ Excellent red light emission is possible, and Pr 3+ After entering the crystal, it will occupy Ca 2+ The charge difference between the two causes defects in the crystal structure, thus providing vacancies for electrons to enter, achieving long-lasting luminescence of red light and UVC;

[0027] (3) Furthermore, the present invention further comprises doping with rare earth element Pr 3+ The matrix is ​​alloyed with Ba2CO3 to obtain a stimuli-responsive single-doped UVC-red dual-band emission material to enhance the emission intensity of the red light band. 2+ Substitute a small amount of Sr in the main matrix 2+ The bond energy strength in the crystal is weakened, making the material △E smaller. The smaller △E makes it easier for UVC emission to undergo non-radiative transitions. The reduction in the probability of UVC emission increases the possibility of red light emission, achieving the enhancement of red light emission, thereby accurately regulating the intensity of the emission in the two bands. This makes the material Na2Sr 1-x Ba x Si2O6:y%Pr 3+ The light emission is more flexible and can be adjusted with Ba 3+ The change of content can be used to regulate the change of luminous intensity in two bands of the material, making the material more controllable. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0029] Figure 1 The X-ray diffraction spectrum of the material prepared in Inventive Example 4;

[0030] Figure 2 The SEM-EDX image of the material prepared in Example 4 of the present invention;

[0031] Figure 3 The XPS full spectrum and O, Sr, Si and Na spectra of the material prepared in Example 4 of the present invention;

[0032] Figure 4 The emission spectrum of the material prepared in Example 4 of the present invention under 245nm light excitation;

[0033] Figure 5 3D emission spectrum of the material prepared in Example 4 of the present invention at 235nm-255nm;

[0034] Figure 6 X-ray diffraction spectra of materials prepared in Examples 1, 2, 3, 4 and 5 of the present invention;

[0035] Figure 7 The emission spectrum of the material prepared in Example 4 of the present invention under 245nm excitation;

[0036] Figure 8 The afterglow attenuation curve of the material prepared in Example 4 of the present invention at 270nm under different X-ray radiation intensities;

[0037] Fig. 9 This is the afterglow decay curve of the material prepared in Example 4 of the present invention at 608nm under X-ray excitation;

[0038] Fig.10 The emission spectrum of the material prepared in Example 4 of the present invention under X-ray;

[0039] Fig.11 The thermal emission spectrum of the material prepared in Example 4 of the present invention at 300°C under X-ray charging;

[0040] Fig.12 X-ray diffraction spectra of materials prepared in Inventive Examples 12-16;

[0041] Fig.13 The emission spectra of the materials prepared in Examples 12-16 of the present invention under 245 nm light excitation;

[0042] Fig.14 The emission spectra of the materials prepared in Examples 12-16 of the present invention under X-ray excitation;

[0043] Fig.15The material prepared in Example 14 of the present invention was arranged into a leaf pattern. After being charged under X-rays for 10 minutes, thermal emission and afterglow photos were taken with an ordinary camera in a dark field, afterglow photos were taken with a UV camera, and then luminescent photos of the material were taken with an ordinary camera (dark field) and a UV camera (bright field) under 245nm light excitation. DETAILED DESCRIPTION

[0044] The present invention will be further described below in conjunction with specific examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0045] The stimuli-responsive single-doped UVC-red light dual-band emitting material prepared in the present invention has the chemical formula: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ ; wherein x=0-0.35, y=0.25-2. The stimuli-responsive single-doped UVC-red light dual-band emission material prepared in the present invention is applied to bright and dark field imaging, solving the problem that inorganic rare earth doped materials can only be used for imaging in dark environments.

[0046] Example 1

[0047] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=0.25, this embodiment 1 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0048] Step 1:

[0049] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 0.25% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0029g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 35min to obtain a raw material mixed powder;

[0050] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0051] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0052] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=0.25.

[0053] Example 2

[0054] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=0.5, this embodiment 2 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0055] Step 1:

[0056] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 0.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0058g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 38min to obtain a raw material mixed powder;

[0057] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0058] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0059] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=0.5.

[0060] Example 3

[0061] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1, this embodiment 3 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0062] Step 1:

[0063] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0115g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 40min to obtain a raw material mixed powder;

[0064] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0065] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0066] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.

[0067] Example 4

[0068] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5, this embodiment 4 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0069] Step 1:

[0070] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0173g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 42min to obtain a raw material mixed powder;

[0071] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0072] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0073] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5.

[0074] Example 5

[0075] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=2, this embodiment 5 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0076] Step 1:

[0077] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 2% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0230g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 44min to obtain a raw material mixed powder;

[0078] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0079] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0080] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=2.

[0081] Example 6

[0082] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+, x=0, y=1.5, this embodiment 6 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0083] Step 1:

[0084] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0173g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 46min to obtain a raw material mixed powder;

[0085] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0086] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 800° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0087] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5.

[0088] Example 7

[0089] The chemical formula of the material provided in this example is Na2Sr 1-x Ba xSi2O6:y%Pr 3+ , x=0, y=1.5, this embodiment 7 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0090] Step 1:

[0091] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0173g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 48min to obtain a raw material mixed powder;

[0092] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0093] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1200° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0094] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5.

[0095] Example 8

[0096] The chemical formula of the material provided in this example is Na2Sr1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5, this embodiment 8 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0097] Step 1:

[0098] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0173g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 50min to obtain a raw material mixed powder;

[0099] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0100] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 2 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0101] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5.

[0102] Example 9

[0103] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5, this embodiment 9 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0104] Step 1:

[0105] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0173g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 52min to obtain a raw material mixed powder;

[0106] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0107] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 4 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0108] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5.

[0109] Example 10

[0110] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5, this embodiment 10 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0111] Step 1:

[0112] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0173g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 54min to obtain a raw material mixed powder;

[0113] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0114] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0115] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 150 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5.

[0116] Embodiment 11

[0117] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0, y=1.5, this embodiment 11 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0118] Step 1:

[0119] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0:1:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7418g Na2CO3, 0g Ba2CO3, 1.0332g Sr2CO3, 0.8410g SiO2 and 0.0173g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 56min to obtain a raw material mixed powder;

[0120] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0121] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0122] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 250 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr3+ , x=0, y=1.5.

[0123] Example 12

[0124] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.05, y=1.5, this embodiment 12 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0125] Step 1:

[0126] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0.05:0.95:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7354g Na2CO3, 0.0685g Ba2CO3, 0.9731g Sr2CO3, 0.8338g SiO2 and 0.0172g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 58min to obtain a raw material mixed powder;

[0127] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0128] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0129] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr1-x Ba x Si2O6:y%Pr 3+ , x=0.05, y=1.5.

[0130] Embodiment 13

[0131] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.1, y=1.5, this embodiment 13 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0132] Step 1:

[0133] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0.1:0.9:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7291g Na2CO3, 0.1357g Ba2CO3, 0.9140g Sr2CO3, 0.8267g SiO2 and 0.0170g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 60min to obtain a raw material mixed powder;

[0134] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0135] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0136] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.1, y=1.5.

[0137] Embodiment 14

[0138] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.15, y=1.5, this embodiment 14 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0139] Step 1:

[0140] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0.15:0.85:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7229g Na2CO3, 0.2019g Ba2CO3, 0.8559g Sr2CO3, 0.8199g SiO2 and 0.0172g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 58min to obtain a raw material mixed powder;

[0141] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0142] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0143] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.15, y=1.5.

[0144] Embodiment 15

[0145] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.2, y=1.5, this embodiment 15 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0146] Step 1:

[0147] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0.2:0.8:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7169g Na2CO3, 0.2669g Ba2CO3, 0.7988g Sr2CO3, 0.8128g SiO2, and 0.0167g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 56min to obtain a raw material mixed powder;

[0148] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0149] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0150] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.2, y=1.5.

[0151] Example 16

[0152] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.25, y=1.5, this embodiment 16 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0153] Step 1:

[0154] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0.25:0.75:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7109g Na2CO3, 0.3309g Ba2CO3, 0.7426g Sr2CO3, 0.8060g SiO2 and 0.0166g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 54min to obtain a raw material mixed powder;

[0155] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0156] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0157] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.25, y=1.5.

[0158] Embodiment 17

[0159] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.3, y=1.5, this embodiment 17 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0160] Step 1:

[0161] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0.3:0.7:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.7050g Na2CO3, 0.3938g Ba2CO3, 0.6874g Sr2CO3, 0.7993g SiO2 and 0.0165g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 52min to obtain a raw material mixed powder;

[0162] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0163] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0164] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.3, y=1.5.

[0165] Embodiment 18

[0166] The chemical formula of the material provided in this example is Na2Sr 1-x Ba x Si2O6:y%Pr 3+, x=0.35, y=1.5, this embodiment 18 provides a method for preparing a stimulus-responsive single-doped UVC-red light dual-band emitting material, comprising the following steps:

[0167] Step 1:

[0168] Na2CO3, Ba2CO3, Sr2CO3, and SiO2 are mixed in a molar ratio of 1:0.35:0.65:2 to obtain a mixture, and then Pr2O3 is added to the mixture, and the proportion of Pr2O3 is 1.5% of the total molar ratio of the mixture; in this embodiment, 0.6992g Na2CO3, 0.4556g Ba2CO3, 0.6330g Sr2CO3, 0.7928g SiO2 and 0.0163g Pr2O3 are weighed and put into an agate mortar, the inner diameter of the selected agate mortar is 110mm, the length of the agate mortar rod is 80mm, and 10ml AR99.7 alcohol is poured into the agate grinding; the raw materials are then ground and mixed for 50min to obtain a raw material mixed powder;

[0169] In this embodiment, 10 ml of AR99.7 alcohol is added to the raw material mixed powder and then mixed. This can make the raw material mixed powder more evenly mixed, and then facilitate the mutual reaction between the raw material mixed powders, so that the prepared material has a higher luminous intensity; the agate mortar has high compressive strength and is resistant to acid and alkali, and can grind many types of raw materials. And after grinding, no mortar body material will be mixed into the ground material, so it can avoid the raw materials being mixed with other impurities during the grinding process, which will affect the final stimulus-responsive dual-emission center color-changing luminescent material; in addition, by limiting the grinding time of the raw materials, each raw material can be ground to a particle size that meets the requirements, and at the same time, the raw materials can be fully and evenly mixed;

[0170] Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 1000° C., the calcination time is 3 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use;

[0171] Step (iii), the calcined product is put into an agate mortar for grinding. The agate mortar used in this step is the same as that in step (i). The calcined product is ground to 200 μm to obtain a stimulus-responsive single-doped UVC-red light dual-band emission material, the chemical formula of which is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0.35, y=1.5.

[0172] Embodiment 19

[0173] See also Fig.15Based on Example 14, this Example 19 provides an application of a responsive single-doped UVC-red light dual-band emission material, wherein the material Na2Sr prepared in Example 4 1-x Ba x Si2O6:y%Pr 3+ , x=0.15, y=1.5, evenly spread on the hollow iron plate, remove the iron sheet to obtain a raw material mixed powder with a leaf pattern and the word "Jiangnan" for imaging application. The stimulus-responsive single-doped UVC-red light dual-band emitting material in Example 14 is arranged into a leaf pattern, and after charging for 10 minutes under X-rays, a normal camera is used to take thermal luminescence and afterglow photos in a dark field, and a UV camera is used to take afterglow photos. Then, under 245nm light excitation, a normal camera (dark field) and a UV camera (bright field) are used to take luminescence photos of the material. The results are as follows: Fig.15 As shown, it shows that the material has good imaging capabilities in bright and dark fields.

[0174] Comparative Analysis

[0175] Experiment 1: The stimulus-responsive single-doped UVC-red dual-band emitting materials obtained in Examples 1-5 were analyzed using an X-ray diffractometer. The results are as follows: Figure 1 and Figure 6 As shown in the figure, the material Na2SrSi2O6:x%Pr 3+ The diffraction pattern of (x = 0.25-2) is almost consistent with the corresponding standard diffraction pattern (PDF#01-074-3938), indicating that at these temperatures and ratios, Pr 3+ The introduction of did not lead to the formation of new phases, confirming that Na2SrSi2O6:x%Pr 3+ (x=0.25-2) Successful synthesis of solid solution.

[0176] Experiment 3: The stimulus responsive single-doped UVC-red dual-band emitting material prepared in Example 4 was tested by SEM-EDX and XPS to obtain Figure 2-3 , it can be seen that the target product was successfully synthesized.

[0177] Experiment 3: The stimulus-responsive single-doped UVC-red dual-band emitting material prepared in Example 4 was excited by a 240nm excitation source to obtain Figure 4 , it can be seen that under the excitation of 245nm ultraviolet light, the whole emits red light and UVC light.

[0178] Experiment 4: The stimulus responsive single-doped UVC-red light dual-band emission material prepared in Example 4 was tested for 3D emission spectrum at 235nm-255nm. The results are as follows: Figure 5As shown, it can be seen that the material is mainly excited in the wavelength range of 235-255nm and emits light in the range of 270-300nm.

[0179] Experiment 5: The stimulus responsive single-doped UVC-red dual-band emission material prepared in the above Examples 1-5 was subjected to spectral testing to obtain the excitation spectrum and emission spectrum. The results are as follows: Figure 7 As shown in the figure, it can be seen that Na2SrSi2O6:x%Pr 3+ (x = 0.25-2) has a consistent emission peak shape under 245nm excitation, and the emission light intensity is the largest when x = 1.5, indicating that the material Pr 3+ The luminescence performance is best when the doping content is 1.5%.

[0180] Experiment 6: The stimulus-responsive single-doped UVC-red dual-band emitting material in Example 4 was charged under X-rays of different radiation intensities for 10 minutes, and the afterglow decay curves of the material at 270nm and 608nm were tested. The results are as follows: Figure 8-9 As shown, it indicates that the material has good afterglow under X-ray charging.

[0181] Experiment 7: The emission spectrum of the stimulus-responsive single-doped UVC-red light dual-band emitting material prepared in Example 4 above was tested under X-ray excitation, as shown in FIG. Fig.10 As shown, it has emission peaks at 270 nm and 608 nm.

[0182] Experiment 8: The stimulus-responsive single-doped UVC-red dual-band emitting material in Example 4 was charged under X-ray for 10 minutes, and the luminescence spectrum of the material was tested at 300°C. The results are as follows: Fig.11 As shown, it means that the material has a red light emission path under X-ray charging.

[0183] Experiment 9: The stimulus-responsive single-doped UVC-red dual-band emitting materials obtained in Examples 12-16 were analyzed using an X-ray diffractometer. The results are as follows: Fig.12 As shown in the figure, the material Na2Sr 1-x Ba x Si2O6:1.5%Pr 3+ The diffraction patterns of (x = 0-0.35) are almost consistent with the corresponding standard diffraction patterns (PDF#01-074-3938), indicating that at these temperatures and ratios, Ba 3+ The alloying of Na2Sr did not induce the formation of new phases, confirming that 1-x Ba x Si2O6:1.5%Pr 3+ (x=0-0.35) Successful synthesis of solid solution.

[0184] Experiment 10: The stimulus-responsive single-doped UVC-red dual-band emitting materials prepared in Examples 12-16 above were excited by 245 nm and X-ray excitation sources to obtain Figure 13-14 It can be seen that under the excitation of 245nm ultraviolet light, the whole emits red light and UVC light, and the luminous intensity of the red light band increases. Under the excitation of X-rays, the luminous intensity of the red light band also increases. At the same time, the luminescence in the ultraviolet region moves from UVC to UVB as X increases, realizing UVC-UVB fluorescence regulation.

[0185] The present invention has been described in detail with reference to the aforementioned embodiments. For those skilled in the art, it is still possible to modify the technical solutions described in the aforementioned embodiments, or to replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A stimulus-responsive single-doped UVC-red light dual-band emitting material, characterized in that: The chemical structure is: Na2Sr 1-x Ba x Si2O6:y%Pr 3+ , x=0~0.35, y=0.25~2.

2. A method for preparing the stimulus responsive single-doped UVC-red light dual-band emitting material according to claim 1, comprising the following steps: Step (i), preparing raw materials, the raw materials include Na2CO3, Sr2CO3, SiO2 and Pr2O3, mixing Na2CO3, Sr2CO3, SiO2 and Pr2O3 according to a proportion, putting them into a mortar, pouring alcohol into the mortar, and then grinding and mixing the raw materials to obtain a raw material mixed powder; Step (ii), placing the raw material mixed powder in a calcination device for calcination, the calcination temperature is 800-1200° C., the calcination time is 2-4 hours, after the calcination is completed, the material is taken out and cooled to room temperature to obtain a calcined material for standby use; Step (iii), putting the calcined product into a mortar for grinding, grinding the calcined product to 150-250 μm, and obtaining the stimulus responsive single-doped UVC-red light dual-band emitting material.

3. The method for preparing the stimulus responsive single-doped UVC-red light dual-band emitting material according to claim 2, characterized in that: In the step (i), Na2CO3, Sr2CO3 and SiO2 are mixed in a molar ratio of 1:1:

2.

4. The method for preparing the stimulus responsive single-doped UVC-red light dual-band emitting material according to claim 2, characterized in that: In the step (i), the proportion of Pr2O3 is 0.25% to 2% of the total molar ratio of the raw material mixed powder.

5. The method for preparing the stimulus responsive single-doped UVC-red light dual-band emitting material according to claim 2, characterized in that: The raw materials in step (a) also include Ba2CO3, and Na2CO3, Ba2CO3, Sr2CO3, SiO2 and Pr2O3 are mixed in proportion, wherein Na2CO3, Ba2CO3, Sr2CO3, SiO2 are mixed in a molar ratio of 1:x:1-x:2, and the proportion of Pr2O3 accounts for 0.25% to 2% of the total molar ratio of the raw material mixed powder.

6. The method for preparing the stimulus responsive single-doped UVC-red light dual-band emitting material according to claim 5, characterized in that: The proportion of Pr2O3 is 1.5% of the total molar ratio of the raw material mixed powder.

7. Application of a stimulus-responsive single-doped UVC-red light dual-band emitting material, characterized in that: The stimulus-responsive single-doped UVC-red light dual-band emitting material of claim 1 is applied to bright-field and dark-field imaging.

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