A multi-color mechanoluminescent phosphor and its preparation method and anti-counterfeiting application

Abstract

The present invention belongs to the field of mechanoluminescent materials and discloses a multi-color mechanoluminescent phosphor and its preparation method and anti-counterfeiting application. The chemical formula of the multi-color mechanoluminescent phosphor is Ca3Ga4O9:xTb 3+ , yEu 3+ ; Among them, 0≤x≤0.03, 0≤y≤0.03, and the crystal structure of the multi-color force-induced luminescent phosphor has non-centrosymmetric characteristics. Due to the non-centrosymmetric characteristics of the Ca3Ga4O9 crystal structure, under the action of pressure, electrons and holes can separate to form a piezoelectric field, which can effectively activate Tb 3+ ions and Eu 3+ ions. By adjusting the doping component Tb 3+ , Eu 3+ The ratio of the two can emit green, yellow, orange, red and other colors of fluorescence under the stimulation of force. This tunable emission color provides greater flexibility and diversity for the use of phosphor materials in anti-counterfeiting applications.

Description

Technical Field

[0001] The invention belongs to the field of mechanoluminescent materials, and in particular relates to a multi-color mechanoluminescent phosphor and a preparation method and anti-counterfeiting application thereof. Background Art

[0002] With economic and social development, the circulation of wealth has accelerated, and counterfeiting and forging of goods, currency, and pharmaceuticals has become increasingly rampant. According to data from the first Global Anti-Counterfeiting Conference, the global value of counterfeit and infringing goods has exceeded $600 billion, equivalent to 7% of global trade. This criminal activity not only harms the investment environment and stifles innovation, but also causes social problems. To combat this illegal and criminal activity, the development of anti-counterfeiting technology is crucial. In this field, mechanoluminescence anti-counterfeiting technology offers significant advantages.

[0003] Mechanoluminescence refers to the phenomenon of luminescence caused by forces such as friction, impact, compression, stretching, bending, twisting, loading, vibration, rubbing, scraping, grinding, crushing, cutting, and splitting. The earliest record of this phenomenon was in Francis Bacon's 1605 book "Advancement of Learning," in which the author observed luminescence when scratching a hard candy bar. The mechanism of mechanoluminescence is currently unclear, but one widely accepted mechanism is based on the piezoelectric effect: when external pressure is applied, the lattice structure of the material changes, causing a shift in charge distribution, which stimulates electrons to jump from low energy levels to higher energy levels, releasing energy and producing luminescence. By exploiting the unique luminescence mechanism of mechanoluminescent materials, highly visible and anti-counterfeiting properties can be created for signs and printed materials. These signs and printed materials can produce a visible luminescence effect when subjected to external forces such as scratching, folding, or pressure, thereby ensuring authenticity and preventing counterfeiting.

[0004] However, the luminescent color of existing mechanoluminescent materials is difficult to control and is relatively single, the anti-counterfeiting effect is relatively general, and the preparation process is relatively complicated, for example, it requires a sintering time of more than 10 hours.

[0005] Therefore, there is an urgent need to provide a mechanoluminescent material with adjustable color and good anti-counterfeiting effect, and further to simplify the preparation process. Summary of the Invention

[0006] The present invention aims to address at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a multi-color force-luminescent phosphor, its preparation method, and anti-counterfeiting applications. The multi-color force-luminescent phosphor of the present invention has tunable emission colors, which provides greater flexibility and versatility in its use in anti-counterfeiting applications, resulting in improved anti-counterfeiting effectiveness. The preparation method of the present invention is simple, low-cost, and non-toxic and pollution-free.

[0007] The inventive concept of the present invention is: the chemical formula of the multi-color mechanoluminescent phosphor of the present invention is Ca3Ga4O9:xTb 3+ , yEu 3+ , where 0≤x≤0.03, 0≤y≤0.03. Due to the non-centrosymmetric characteristics of the Ca3Ga4O9 crystal structure, under the action of pressure, electrons and holes can separate to form a piezoelectric field, which can effectively activate Tb 3+ ions and Eu 3+ ions. By adjusting the doping component Tb 3+ , Eu 3+ The ratio of the two can emit green, yellow, orange, red and other colors of fluorescence under the stimulation of force. This tunable emission color provides greater flexibility and diversity for the use of phosphor materials in anti-counterfeiting applications.

[0008] A first aspect of the present invention provides a multi-color mechanoluminescent phosphor.

[0009] Specifically, a multi-color mechanoluminescent phosphor, whose chemical formula is Ca3Ga4O9:xTb 3+ , yEu 3+ ; Wherein, 0≤x≤0.03, 0≤y≤0.03, and the crystal structure of the multi-color force-induced luminescent phosphor has a non-centrosymmetric characteristic.

[0010] Preferably, the value range of x is 0≤x≤0.02.

[0011] Preferably, the value range of y is 0≤y≤0.02.

[0012] Preferably, the chemical formula of the multi-color mechanoluminescent phosphor is Ca3Ga4O9:0.03Tb 3+ 、Ca3Ga4O9:0.03Tb 3+ ,0.01Eu 3+ 、Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ 、Ca3Ga4O9:0.03Tb 3+ , 0.03Eu 3+ or Ca3Ga4O9:0.03Eu3+ .

[0013] Preferably, Tb in the multi-color mechanoluminescent phosphor 3+ The doping amount is 0.00-0.03mmol.

[0014] Preferably, the multi-color mechanoluminescent phosphor contains Eu 3+ The doping amount is 0.00-0.03mmol.

[0015] Preferably, Tb in the multi-color mechanoluminescent phosphor 3+ The doping amount and Eu 3+ The sum of the doping amounts is greater than 0 mmol.

[0016] Preferably, the multi-color mechanoluminescent phosphor generates a line spectrum within a wavelength range of 450 nm to 720 nm under the action of force.

[0017] Preferably, the multi-color mechanoluminescent phosphor is of an orthorhombic crystal system.

[0018] Preferably, the multi-color mechanoluminescent phosphor has piezoelectricity.

[0019] Preferably, the colors of light emitted by the multi-color mechanoluminescent phosphor include green, yellow, orange, red, cyan, blue, purple and other colors.

[0020] A second aspect of the present invention provides a method for preparing a multi-color mechanoluminescent phosphor.

[0021] Specifically, a method for preparing a multi-color mechanoluminescent phosphor comprises the following steps:

[0022] According to the stoichiometric ratio of the chemical formula of the multi-color force-induced luminescent phosphor, a calcium source, a gallium source, a terbium source and a europium source are mixed to obtain a mixture, and the mixture is calcined to prepare the multi-color force-induced luminescent phosphor.

[0023] Preferably, the calcium source, gallium source, terbium source, and europium source include calcium oxide, gallium oxide, terbium oxide, and europium oxide or salt.

[0024] Preferably, the calcium source is CaCO3.

[0025] Preferably, the gallium source is Ga2O3.

[0026] Preferably, the terbium source is Tb4O7.

[0027] Preferably, the europium source is Eu2O3.

[0028] Preferably, the calcination is carried out in an air atmosphere.

[0029] Preferably, the calcination temperature is 1100-1300° C., and the calcination temperature is 5h-8h; further preferably, the calcination temperature is 1200-1300° C., and the calcination temperature is 6h-8h.

[0030] A third aspect of the present invention provides an application of a multi-color mechanoluminescent phosphor.

[0031] An anti-counterfeiting product comprises the above-mentioned multi-color force-luminescent fluorescent powder.

[0032] Preferably, the anti-counterfeiting product is a product with an anti-counterfeiting function, comprising an anti-counterfeiting label.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The chemical formula of the multi-color mechanoluminescent phosphor of the present invention is Ca3Ga4O9:xTb 3+ , yEu 3+ , where 0≤x≤0.03, 0≤y≤0.03. Due to the non-centrosymmetric characteristics of the Ca3Ga4O9 crystal structure, under the action of pressure, electrons and holes can separate to form a piezoelectric field, which can effectively activate Tb 3+ ions and Eu 3+ ions. By adjusting the doping component Tb 3+ , Eu 3+ The ratio of the two can emit green, yellow, orange, red and other colors of fluorescence under the stimulation of force. This tunable emission color provides greater flexibility and diversity for the use of phosphor materials in anti-counterfeiting applications.

[0035] (2) The multi-color mechanoluminescent phosphor of the present invention is derived from Tb 3+ of 5 D4- 7 F J and Eu 3+ of 5 D0- 7 F J (J=1,2,3,4) transition luminescence, based on the piezoelectric effect, can generate excitation energy under the action of force. This phosphor has the advantages of simple preparation, readily available and inexpensive raw materials, and a non-toxic and pollution-free preparation process. Furthermore, the color of the mechanoluminescence can be tuned, providing greater flexibility and versatility in the use of phosphors in anti-counterfeiting applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention. 3+ , 0.02Eu 3+Comparison of X-ray diffraction pattern and standard card (ICSD#100356Ca3Ga4O9);

[0037] Figure 2 This is the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention. 3+ , 0.02Eu 3+ Schematic diagram of the crystal structure of Ca3Ga4O9;

[0038] Figure 3 The multi-color mechanoluminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention was characterized by using an atomic force microscope. 3 + , 0.02Eu 3+ Detected piezoelectric phase curve;

[0039] Figure 4 The multi-color mechanoluminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention was characterized by using an atomic force microscope. 3 + , 0.02Eu 3+ Detected amplitude curve;

[0040] Figure 5 To measure the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 1 under 50N stress conditions 3+ Example 2 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.01Eu 3+ Example 3 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ Example 4 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.03Eu 3+ Example 5 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Eu 3+ Mechanoluminescence spectrum of

[0041] Figure 6 The multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb of Example 1 3+ Example 2 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.01Eu 3+ Example 3 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ Example 4 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb3+ , 0.03Eu 3+ Example 5 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Eu 3+ The color coordinates corresponding to the luminous color;

[0042] Figure 7 This is the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 5 of the present invention. 3+ , 0.02Eu 3+ Anti-counterfeiting label made by mixing with polydimethylsiloxane elastomer and its application demonstration. DETAILED DESCRIPTION

[0043] In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the following examples are given for illustration. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.

[0044] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0045] Example 1: Preparation of multi-color mechanoluminescent phosphor

[0046] A multi-color mechanoluminescent phosphor with the chemical formula of Ca3Ga4O9:0.03Tb 3+ , and the crystal structure of the multi-color force-luminescent phosphor has non-centrosymmetric characteristics.

[0047] A method for preparing a multi-color mechanoluminescent phosphor comprises the following steps:

[0048] 0.6005 g of CaCO3, 0.7498 g of Ga2O3, and 0.0112 g of Tb4O7 were weighed according to the elemental stoichiometric ratio and ground in an agate mortar for 15 minutes to uniformly mix the raw materials to obtain a mixture. The mixture was then placed in a corundum crucible, placed in a muffle furnace, and calcined at 1300°C in an air atmosphere for 360 minutes (i.e., 6 hours). The mixture was then cooled to room temperature to obtain a multicolor force-induced luminescent phosphor.

[0049] The multi-color force-induced luminescence phosphor emits green light under stress stimulation.

[0050] Example 2: Preparation of multi-color mechanoluminescent phosphor

[0051] A multi-color mechanoluminescent phosphor with the chemical formula of Ca3Ga4O9:0.03Tb 3+ , 0.01Eu 3+ , and the crystal structure of the multi-color force-luminescent phosphor has non-centrosymmetric characteristics.

[0052] A method for preparing a multi-color mechanoluminescent phosphor comprises the following steps:

[0053] 0.6005 g of CaCO3, 0.7498 g of Ga2O3, 0.0112 g of Tb4O7, and 0.0035 g of Eu2O3 were weighed according to the elemental stoichiometric ratio, and the raw materials were ground in an agate mortar for 15 minutes to uniformly mix the raw materials to obtain a mixture. The mixture was placed in a corundum crucible, placed in a muffle furnace, and calcined at 1300°C in an air atmosphere for 360 minutes (i.e., 6 hours). After cooling to room temperature, a multi-color force-induced luminescent phosphor was obtained.

[0054] The phosphor emits yellow-green light under stress stimulation.

[0055] Example 3: Preparation of multi-color mechanoluminescent phosphor

[0056] A multi-color mechanoluminescent phosphor with the chemical formula of Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ , and the crystal structure of the multi-color force-luminescent phosphor has non-centrosymmetric characteristics.

[0057] A method for preparing a multi-color mechanoluminescent phosphor comprises the following steps:

[0058] 0.6005 g of CaCO3, 0.7498 g of Ga2O3, 0.0112 g of Tb4O7, and 0.0070 g of Eu2O3 were weighed according to the elemental stoichiometric ratio, and the raw materials were ground in an agate mortar for 15 minutes to uniformly mix the raw materials to obtain a mixture. The mixture was charged into a corundum crucible, placed in a muffle furnace, calcined at 1300°C in an air atmosphere for 360 minutes, and then cooled to room temperature to obtain a multi-color force-induced luminescent phosphor.

[0059] The phosphor emits orange light under stress stimulation.

[0060] Example 4: Preparation of multi-color mechanoluminescent phosphor

[0061] A multi-color mechanoluminescent phosphor with the chemical formula of Ca3Ga4O9:0.03Tb 3+ , 0.03Eu 3+ , and the crystal structure of the multi-color force-luminescent phosphor has non-centrosymmetric characteristics.

[0062] A method for preparing a multi-color mechanoluminescent phosphor comprises the following steps:

[0063] 0.6005 g of CaCO3, 0.7498 g of Ga2O3, 0.0112 g of Tb4O7, and 0.0105 g of Eu2O3 were weighed according to the elemental stoichiometric ratio, and the raw materials were ground in an agate mortar for 15 minutes to uniformly mix the raw materials to obtain a mixture. The mixture was placed in a corundum crucible, placed in a muffle furnace, and calcined at 1300°C in an air atmosphere for 360 minutes (i.e., 6 hours). After cooling to room temperature, a multi-color force-induced luminescent phosphor was obtained.

[0064] The phosphor emits orange-red light under stress stimulation.

[0065] Example 5: Preparation of multi-color mechanoluminescent phosphor

[0066] A multi-color mechanoluminescent phosphor with the chemical formula of Ca3Ga4O9:0.03Eu 3+ , and the crystal structure of the multi-color force-luminescent phosphor has non-centrosymmetric characteristics.

[0067] A method for preparing a multi-color mechanoluminescent phosphor comprises the following steps:

[0068] 0.6005 g of CaCO3, 0.7498 g of Ga2O3, 0.0112 g of Tb4O7, and 0.0105 g of Eu2O3 were weighed according to the elemental stoichiometric ratio, and the raw materials were ground in an agate mortar for 15 minutes to uniformly mix the raw materials to obtain a mixture. The mixture was placed in a corundum crucible, placed in a muffle furnace, and calcined at 1300°C in an air atmosphere for 360 minutes (i.e., 6 hours). After cooling to room temperature, a multi-color force-induced luminescent phosphor was obtained.

[0069] The phosphor emits red light under stress stimulation.

[0070] Example 6: Preparation of anti-counterfeiting labels

[0071] A method for preparing an anti-counterfeiting label comprises the following steps:

[0072] 1g of Ca3Ga4O9:0.03Tb prepared in Example 3 3+ , 0.02Eu 3+ The multi-color force-induced luminescent phosphor was mixed with 2g of polydimethylsiloxane elastomer, and 0.1g of curing agent (Kandao Ning DC184 original PDMS polymethylsiloxane special curing agent) was added. The mixture was stirred with a magnetic stirrer for 20 minutes to fully mix the mixture. The mixture was poured into a mold and heated at 150°C for 20 minutes to accelerate the curing to obtain an anti-counterfeiting label.

[0073] Comparative Example

[0074] The comparative example is the literature "Hu T, Gao Y, Wang B, et al. A new class of battery-free, mechanically powered, piezoelectric Ca5Ga6O 14 :Tb 3+ Ca5Ga6O in phosphors with self-recoverable luminescence[J].Journal of Materials Chemistry C, 2022,10(25):9554-9562" 14 :Tb 3+ .

[0075] From the literature "Hu T, Gao Y, Wang B, et al. A new class of battery-free, mechanically powered, piezoelectric Ca5Ga6O 14 :Tb 3+ Ca5Ga6O in phosphors with self-recoverable luminescence[J].Journal of Materials Chemistry C, 2022,10(25):9554-9562" 14 :0.02Tb 3+ The XRD diffraction pattern shows that Ca5Ga6O 14 :0.02Tb 3+ The diffraction peaks of Ca3Ga4O9:0.03Tb prepared in Example 3 of the present invention are similar to those of 3+ , 0.02Eu 3+ The diffraction peaks (such as Figure 1 This indicates that the crystal structures of the two are different.

[0076] From the literature "Hu T, Gao Y, Wang B, et al. A new class of battery-free, mechanically powered, piezoelectric Ca5Ga6O 14 :Tb 3+ Ca5Ga6O in phosphors with self-recoverable luminescence[J].Journal of Materials Chemistry C, 2022,10(25):9554-9562" 14:0.02Tb 3+ It can be seen from the mechanoluminescence emission spectrum that its emission peak is only Tb 3+ The characteristic emission of the ion proves that its luminescence color is single and has no tunable emission color.

[0077] Product effect testing

[0078] Figure 1 This is the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention. 3+ , 0.02Eu 3+ Comparison of X-ray diffraction pattern and standard card (ICSD#100356Ca3Ga4O9); Figure 1 It can be seen that the multi-color force-induced luminescence phosphor Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ The physical phase can match the standard card.

[0079] Figure 2 This is the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention. 3+ , 0.02Eu 3+ Schematic diagram of the crystal structure of Ca3Ga4O9; Figure 2 It can be seen that Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ The structure belongs to the orthorhombic crystal system.

[0080] Figure 3 The multi-color mechanoluminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention was characterized by using an atomic force microscope. 3 + , 0.02Eu 3+ Detected piezoelectric phase curve;

[0081] Figure 4 The multi-color mechanoluminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention was characterized by using an atomic force microscope. 3 + , 0.02Eu 3+ Detected amplitude curve;

[0082] Figure 5 To measure the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 1 under 50N stress conditions 3+ Example 2 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.01Eu 3+Example 3 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ Example 4 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.03Eu 3+ Example 5 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Eu 3+ Mechanoluminescence spectrum of

[0083] Figure 6 The multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb of Example 1 3+ Example 2 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.01Eu 3+ Example 3 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ Example 4 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.03Eu 3+ Example 5 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Eu 3+ The color coordinates corresponding to the luminous color;

[0084] Figure 7 This is the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 5 of the present invention. 3+ , 0.02Eu 3+ Anti-counterfeiting label made by mixing with polydimethylsiloxane elastomer and its application demonstration.

[0085] from Figure 3 and Figure 4 It can be seen that the phase lag of the piezoelectric phase curve and the butterfly amplitude of the amplitude curve verify that Ca3Ga4O9:0.03Tb 3+ , 0.02Eu 3+ The piezoelectric response and polarization behavior of the phosphor prepared in the embodiment of the present invention can be explained from this that the mechanoluminescence of the phosphor prepared in the embodiment of the present invention is electroluminescence caused by piezoelectricity.

[0086] The optical fiber spectrometer of Ocean Optics was used to measure the multi-color mechanoluminescent phosphor Ca3Ga4O9:0.03Tb in Example 1 under 50N stress. 3+ Example 2 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.01Eu 3+ Example 3 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Tb 3+, 0.02Eu 3+ Example 4 Multicolor Mechanoluminescent Phosphor Ca3Ga4O9:0.03Tb 3+ , 0.03Eu 3+ Example 5 Multicolor force-induced luminescent phosphor Ca3Ga4O9:0.03Eu 3+ The mechanoluminescence spectrum of Figure 5 As shown, from Figure 5 It can be seen that the luminescence is due to Tb 3+ of 5 D4- 7 F J and Eu 3+ of 5 D0- 7 F J The spectral intensity of each of them changes with the concentration, causing the color of the luminescent material to gradually change from green to red. The emission color coordinates of the phosphors prepared in the five examples are as follows: Figure 6 As shown, green, yellow-green, orange, orange-red, and red light are emitted respectively.

[0087] like Figure 7 The functionality of the security label was verified as shown. The capital letters "ML" were written on the security label prepared in Example 6 using an object similar in shape to a pen and recorded using a camera under exposure conditions. The invisible "ML" signal was clearly visible. Therefore, this encrypted security label has the potential to further enhance the security level of mechanoluminescence-based encryption anti-counterfeiting technology.

[0088] Table 1 is a graph showing the multi-color force-induced luminescent phosphor Ca3Ga4O9:0.03Tb in Example 3 of the present invention. 3+ , 0.02Eu 3+ The piezoelectric strain constant matrix calculated for the Ca3Ga4O9 crystal in the figure has the piezoelectric strain tensor d ij The five independent components d 31 d 32 d 33 d 15 d 24 , the maximum value reaches 11.89pm / V. Based on this calculation result, it can be concluded that Ca3Ga4O9 is a piezoelectric compound.

[0089] Table 1

[0090]

[0091] The above specific embodiments further illustrate the objectives, technical solutions, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the scope of protection of the present invention. In particular, it should be noted that any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention for those skilled in the art.

Claims

1. Application of a phosphor as a multi-color mechanoluminescent material, characterized in that: The chemical formula of the phosphor is Ca3Ga4O9: xTb 3+ , yEu 3+ ; Wherein, 0<x≤0.03, 0<y≤0.03, and the crystal structure of the phosphor has non-centrosymmetric characteristics.

2. The use according to claim 1, characterized in that The value range of x is 0<x≤0.02; and / or the value range of y is 0<y≤0.

02.

3. The use according to claim 1, characterized in that The chemical formula of the phosphor is Ca3Ga4O9:0.03Tb 3+ ,0.01Eu 3+ 、Ca3Ga4O9: 0.03Tb 3+ , 0.02Eu 3+ or Ca3Ga4O9: 0.03Tb 3+ , 0.03Eu 3+ .

4. The use according to claim 1, characterized in that The phosphor generates a line spectrum within a wavelength range of 450 nm to 720 nm under the action of force.

5. The use according to claim 1, characterized in that The phosphor is of an orthorhombic crystal system; and / or the phosphor has piezoelectricity.

6. The use according to any one of claims 1 to 5, characterized in that The preparation method of the phosphor comprises the following steps: According to the stoichiometric ratio of the chemical molecular formula of the phosphor, a calcium source, a gallium source, a terbium source and a europium source are mixed to obtain a mixture, and the mixture is calcined to obtain the phosphor.

7. The use according to claim 6, characterized in that The calcium source, gallium source, terbium source and europium source include calcium oxide, gallium oxide, terbium oxide and europium oxide or salt; and / or the calcination temperature is 1100-1300° C. and the calcination temperature is 5h-8h.

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