A multi-color electroluminescent film based on phosphor and its preparation method and application

Abstract

The application discloses a multi-color mechanoluminescence film based on fluorescent powder and a preparation method and application thereof, and the preparation method comprises the following steps: preparing a series of light-color-adjustable mechanoluminescence materials through a high-temperature solid-phase method, and then compounding the prepared mechanoluminescence materials with polyvinyl alcohol to prepare a flexible transparent film, and the color change of cyan-yellow-orange red can be clearly observed by writing the numbers '1', '2' and '3' on the transparent film, which indicates that the prepared mechanoluminescence material has great potential in application fields such as electronic signature and anti-counterfeiting.

Description

Technical Field

[0001] This invention belongs to the field of mechanoluminescent materials technology, specifically relating to a multicolor mechanoluminescent thin film based on phosphor, its preparation method, and its application. Background Technology

[0002] Light is fundamental to the survival and development of any living organism, a crucial medium for communication with nature, and a carrier of information. With the continuous development and progress of human society and technology, our understanding of light has become increasingly thorough. Simultaneously, the development and demands of various emerging applications have further fueled our enthusiasm for finding new luminescent materials. Luminescence is a special phenomenon, a result of the interaction between external influences and matter. Based on different excitation methods, luminescence phenomena can be classified into photoluminescence, electroluminescence, mechanoluminescence, chemiluminescence, bioluminescence, and pyroluminescence. Compared to other luminescence phenomena, mechanoluminescence is a special one. Although mechanoluminescence has been recorded for a long time, its mechanism remains incomplete, hindering the further development and practical application of mechanoluminescent materials. Therefore, researching mechanoluminescent materials with excellent luminescent properties and further exploring their intrinsic mechanisms is particularly important.

[0003] Mechatronics refers to the process by which a material emits light in response to various mechanical stimuli, such as compression, stretching, friction, and impact. Compared to photoluminescent and electroluminescent materials, mechatronic materials can emit light directly in response to appropriate external mechanical stimuli, without relying on light or electrical excitation. Due to this unique property, mechatronic materials have enormous application potential in fields such as visual sensing, information storage, visual expression, pressure sensors, and organic piezoelectric display devices. Specifically, they can be used for real-time and multidimensional stress-mechanical sensing. Over the past 20 years, researchers have focused on developing mechatronic materials with a variety of properties, including high mechanical sensitivity, high brightness, wide emission wavelength, excellent luminescence repeatability, and significant stability.

[0004] With the development of the field of mechanoluminescence, exploring novel mechanoluminescent materials (including matrix materials and doped ions) has become a major breakthrough in this research direction. CaZnOS semiconductor materials have gradually become a research hotspot due to their excellent piezoelectric and luminescent properties and simple preparation process. In addition, benefiting from the rapid development of heterojunction engineering, semiconductor heterojunctions have a strong positive effect on carrier transport at the interface and can regulate luminescence behavior.

[0005] Therefore, this invention provides a multicolor mechanoluminescent thin film based on phosphor, its preparation method, and its application. Summary of the Invention

[0006] The purpose of this invention is to provide a multicolor mechanoluminescent thin film based on phosphor, its preparation method, and its applications. A series of Bi-based films were successfully prepared by a high-temperature solid-state synthesis method. 3+ and Mn 2+ Co-doped ZnS / CaZnOS heterojunction mechanoluminescent materials, by changing Mn 2+ The doping ratio was adjusted to achieve controllable adjustment of the emission color from cyan to white to orange-red. Furthermore, a flexible transparent film was prepared by combining the mechanoluminescent material with polyvinyl alcohol, and the mechanoluminescent properties of the material were explored. The raw materials used in this invention are environmentally friendly, inexpensive, and readily available. By combining mechanical force and light emission, the conversion from mechanical energy to light energy is achieved, which holds promise for numerous novel applications.

[0007] The first aspect of the present invention provides a multicolor mechanoluminescent phosphor.

[0008] Specifically, a multicolor mechanoluminescent phosphor has the composition ZnS / Ca 0.96 ZnOS: 2% Bi, x% Mn (x=0, 0.05, 0.1, 0.2, 0.4, 0.7, 1, 2, 4, 8), 2% Li.

[0009] A second aspect of the present invention provides a multicolor mechanoluminescent thin film based on phosphor, a method for preparing the same, and its application.

[0010] Specifically, the present invention proposes the following technical solution: a multicolor mechanoluminescent thin film based on phosphor, its preparation method and application, comprising the following steps:

[0011] (1) Weigh the required raw materials (CaCO3, ZnS, MnCO3, Bi2O3, Li2CO3) according to the calculated molar percentage and add them to the agate mortar in sequence.

[0012] (2) Add an appropriate amount of ethanol to the sample weighed in step (1), grind it in an agate mortar until the ethanol is completely evaporated, and dry it in a vacuum drying oven.

[0013] (3) Transfer the powder obtained in step (2) into a crucible, and place the crucible in a tube furnace for high-temperature calcination with argon as a protective gas to obtain the heterojunction mechanoluminescent material (ZnS / CaZnSO:Bi). 3+ ,Mn 2+ ).

[0014] (4) Prepare a polyvinyl alcohol (PVA) film that can generate light through friction using the mechanoluminescent material obtained in step (3). First, prepare a 10% polyvinyl alcohol solution. Then, weigh a certain amount of mechanoluminescent material, mix it with the polyvinyl alcohol solution, and use an ultrasonic cell disruptor to mix the two thoroughly. Pour the prepared solution into a petri dish and dry it in an oven to obtain a polyvinyl alcohol mechanoluminescent film.

[0015] Preferably, the ZnS / Ca prepared in step (1) 0.96 ZnOS: 2% Bi, x% Mn (x=0, 0.05, 0.1, 0.2, 0.4, 0.7, 1, 2, 4, 8), 2% Li using Bi 3+ and Mn 2+ Double doping, by changing Mn 2+ To obtain better fluorescent materials, concentration can be adjusted.

[0016] Preferably, in step (2), the grinding time in the agate mortar is 15-30 min, and the drying conditions are drying in a vacuum drying oven at 60°C for 30 min.

[0017] Preferably, the high-temperature calcination process in step (3) is to heat from room temperature (25°C) to 800°C and hold for 1 hour, then heat from 800°C to 1100°C and hold for 4 hours, then end the process and let it cool naturally to room temperature.

[0018] Preferably, the polyvinyl alcohol used in step (4) is type 1788. The mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol solution obtained in step (4) is 1:10. The polyvinyl alcohol is slowly added to the deionized water at 90°C. The concentration of the prepared polyvinyl alcohol solution is 10%.

[0019] Preferably, the oven conditions in step (4) are to dry at 60°C for 8-10 hours to finally obtain a polyvinyl alcohol mechanoluminescent film.

[0020] The present invention also provides a multicolor mechanoluminescent thin film based on phosphor as described above, its preparation method and application.

[0021] Compared with the prior art, the beneficial effects of the present invention are:

[0022] 1. The CIE chromaticity diagram shows that as Mn... 2+ With increasing doping levels, the emission color can be controllably adjusted from cyan to white to orange-red. Furthermore, monitoring the thermal stability of the resulting luminescent material reveals that the color gradually changes from cyan to white to orange-red as the temperature rises, demonstrating its potential application value in temperature sensing and anti-counterfeiting fields.

[0023] 2. The prepared mechanoluminescent material was composited with polyvinyl alcohol to form a flexible transparent film. By writing the numbers "1", "2", and "3" on the transparent film, the color change from cyan to yellow to orange-red could be clearly observed. This indicates that the prepared mechanoluminescent material has great potential in applications such as electronic signatures and anti-counterfeiting.

[0024] 3. The raw materials used in this invention are environmentally friendly, inexpensive, and readily available. By combining mechanical force and light emission, the conversion from mechanical energy to light energy is realized, which is expected to be applied to many new applications.

[0025] The above is an overview of the technical solution. The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0026] To clearly illustrate the technical solutions of the present invention, the following will briefly introduce the implementation process and the drawings used in the embodiments. The following drawings only show some embodiments of the present invention and should not be regarded as any form of limitation on the present invention.

[0027] Figure 1 Different Mn preparations were performed in Examples 1-10 2+ Doping concentration of ZnS / CaZnOS: 2% Bi 3+ ,x%Mn 2+ The emission spectrum.

[0028] Figure 2 Different Mn preparations were performed in Examples 1-10 2+ Doping concentration of ZnS / CaZnOS: 2% Bi 3+ ,x%Mn 2+ The CIE chromaticity diagram.

[0029] Figure 3 Mn in Example 11 2+ Images of handwriting on transparent PVA films prepared from samples with concentrations of 0%, 0.2%, and 2%, showing the characters “1”, “2”, and “3” written in sequence. Detailed Implementation

[0030] The technical solution of the present invention will be further described below with reference to specific embodiments and accompanying drawings. However, the following embodiments are only for enhancing the description of the technical solution of the present invention and should not be construed as any limitation on the scope of the invention as claimed.

[0031] Example 1

[0032] Weigh 0.0466g Bi2O3, 0.96g CaCO3, 2.4361g ZnS and 0.00739g LiCO3 (without MnCO3 doping), and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0033] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that in Mn 2+ As the doping concentration increases from 0% to 8%, a cyan emission peak at 479 nm and a red emission peak at around 590 nm are observed. It can be observed that as the Mn content increases... 2+ With the continuous increase of doping concentration, Bi at 479 nm 3+ The intensity of the emission peak continuously decreases, with Mn located at 590 nm. 2+ The intensity of the emission peak first increases and then decreases.

[0034] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, without Mn doping 2+ At that time, its CIE coordinates are (0.1615, 0.2379).

[0035] Example 2

[0036] Weigh 0.0466g Bi2O3, 0.96g CaCO3, 2.4349g ZnS, 0.00739g LiCO3 and 0.00144g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0037] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 0.05%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, and the Mn at 590 nm... 2+ The intensity of the emission peak is enhanced.

[0038] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 0.05%, its CIE coordinates are (0.1754, 0.2495).

[0039] Example 3

[0040] Weigh 0.0466g Bi2O3, 0.96g CaCO3, 2.4337g ZnS, 0.00739g LiCO3 and 0.00287g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0041] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 0.1%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, and the Mn at 590 nm... 2+ The intensity of the emission peak is enhanced.

[0042] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn2+ When the concentration is 0.1%, its CIE coordinates are (0.2026, 0.2730).

[0043] Example 4

[0044] Weigh 0.0466g Bi2O3, 0.96g CaCO3, 2.4312g ZnS, 0.00739g LiCO3 and 0.00575g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0045] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 0.2%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, and the Mn at 590 nm... 2+ The intensity of the emission peak is enhanced.

[0046] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 0.2%, its CIE coordinates are (0.2410, 0.2948).

[0047] Example 5

[0048] Weigh 0.0466g Bi2O3, 0.96g CaCO3, 2.4264g ZnS, 0.00739g LiCO3 and 0.0115g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0049] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 0.4%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, and the Mn at 590 nm... 2+ The intensity of the emission peak is enhanced.

[0050] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 0.4%, its CIE coordinates are (0.3269, 0.3441).

[0051] Example 6

[0052] Weigh 0.0466g Bi2O3, 0.96g CaCO3, 2.4190g ZnS, 0.00739g LiCO3 and 0.02g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0053] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 0.7%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, and the Mn at 590 nm... 2+ The intensity of the emission peak is enhanced.

[0054] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 0.7%, its CIE coordinates are (0.4671, 0.4106).

[0055] Example 7

[0056] Weigh 0.0466g Bi2O3, 0.96g CaCO3, 2.4118g ZnS, 0.00739g LiCO3 and 0.0287g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0057] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 1%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, and the Mn at 590 nm... 2+ The intensity of the emission peak is enhanced.

[0058] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 1%, its CIE coordinates are (0.5051, 0.4232).

[0059] Example 8

[0060] Weigh 0.0575g Bi2O3, 0.96g CaCO3, 2.3874g ZnS, 0.00739g LiCO3 and 0.0287g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0061] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 2%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, at which point Mn is located at 590 nm. 2+ The intensity of the emission peak reaches its maximum.

[0062] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 2%, its CIE coordinates are (0.5447, 0.4391).

[0063] Example 9

[0064] Weigh 0.115g Bi2O3, 0.96g CaCO3, 2.339g ZnS, 0.00739g LiCO3 and 0.0287g MnCO3, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0065] The prepared sample ZnS / CaZnOS:Bi3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 4%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, at which point Mn is located at 590 nm. 2+ The intensity of the emission peak begins to decrease.

[0066] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 4%, its CIE coordinates are (0.5550, 0.4160).

[0067] Example 10

[0068] Weigh 0.23g Bi₂O₃, 0.96g CaCO₃, 2.241g ZnS, 0.00739g LiCO₃, and 0.0287g MnCO₃, and add them sequentially to an agate mortar. Add an appropriate amount of ethanol and grind in the agate mortar for 15-30 minutes until the ethanol is completely evaporated. Dry in a vacuum drying oven at 60℃ for 30 minutes. Transfer the resulting powder to a crucible and place the crucible in a tube furnace. Calcinate at high temperature using argon as a protective gas. The specific heating program includes heating from room temperature (25℃) to 800℃ and holding for 1 hour, then heating from 800℃ to 1100℃ and holding for 4 hours. End the program and allow it to cool naturally to room temperature. Grind the sintered product into powder for later testing and characterization.

[0069] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ emission spectrum such as Figure 2 As shown. By Figure 2 It can be seen that when Mn is added 2+ At a concentration of 8%, Bi is located at 479 nm. 3+ The intensity of the emission peak decreases, at which point Mn is located at 590 nm. 2+ The intensity of the emission peak continued to decrease.

[0070] The prepared sample ZnS / CaZnOS:Bi 3+ Mn 2+ The CIE chromaticity diagram is as follows Figure 3 As shown. By Figure 3 It can be seen that, when doped with Mn 2+ When the concentration is 8%, its CIE coordinates are (0.5407, 0.4247).

[0071] Example 11

[0072] After obtaining the three groups of Mn in Examples 1, 4, and 8 2+ After preparing three groups of samples with doping concentrations of 0%, 0.2%, and 2%, 20g of each group of polyvinyl alcohol (PVA) 1788 was slowly added to 200g of deionized water at 90℃ to prepare a 10% PVA solution. Then, the three groups of mechanoluminescent materials were weighed, mixed with the PVA solution, and thoroughly mixed using an ultrasonic cell disruptor. The prepared solution was then poured into a petri dish and dried in an oven at 60℃ for 8-10 hours to obtain three groups of PVA mechanoluminescent films.

[0073] By securing a transparent polyvinyl alcohol film to a table with transparent tape, one person writes on the film while another person takes photos and videos of the writing process, obtaining images of the handwriting. The numbers "1", "2", and "3" were written in sequence, and "123" is clearly visible in the images. Figure 1 As shown, simultaneously with Mn 2+ The color gradually deepens as the doping concentration of Mn increases, indicating that the color can be controlled by adjusting the doping concentration of Mn. 2+ The doping concentration allows for the control of the mechanoluminescence color. Simultaneously, the prepared polyvinyl alcohol film can record the signatures or handwriting habits of different users, and can be analyzed specifically by varying the applied stress.

[0074] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A multicolor mechanoluminescent thin film based on phosphor, characterized in that, The film is composed of two components, A and B. Component A is a phosphor prepared by mixing CaCO3, ZnS, MnCO3, Bi2O3, and Li2CO3; Component B is a polyvinyl alcohol solution of type 1788 with a concentration of 10%; Preparation of phosphor component A (1) Weigh the required raw materials CaCO3, ZnS, MnCO3, Bi2O3 and Li2CO3 according to the calculated molar percentage and add them to the agate mortar in sequence; (2) Add an appropriate amount of ethanol to the sample obtained in step (1), grind it in an agate mortar until the ethanol is completely evaporated, and dry it in a vacuum drying oven; (3) The powder obtained in step (2) is transferred into a crucible, and the crucible is placed into a tube furnace for high-temperature calcination to obtain a heterojunction mechanical luminescent material ZnS / CaZnOS:Bi under protection of argon gas 3+ , Mn 2+ ; Preparation of a multicolor mechanoluminescent thin film based on phosphor (4) Add the mechanoluminescent material obtained in step (3) to a 10% polyvinyl alcohol solution, mix the two thoroughly using an ultrasonic cell disruptor, pour the resulting mixed solution into a petri dish and dry it in an oven to obtain a polyvinyl alcohol mechanoluminescent film.

2. The multicolor mechanoluminescent thin film based on phosphor according to claim 1, characterized in that: The ZnS / Ca prepared in step (1) 0.96 ZnOS: 2% Bi, x% Mn, 2% Li phosphor, specifically Mn 2+ The doping concentrations are x = 0, 0.05, 0.1, 0.2, 0.4, 0.7, 1, 2, 4, 8.

3. The multicolor mechanoluminescent thin film based on phosphor according to claim 1, characterized in that: In step (2), the grinding time in the agate mortar is 15-30 minutes, and the drying conditions are drying in a vacuum drying oven at 60°C for 30 minutes.

4. The multicolor mechanoluminescent thin film based on phosphor according to claim 1, characterized in that: The high-temperature calcination process in step (3) is to heat from 25°C to 800°C and hold for 1 hour, then heat from 800°C to 1100°C and hold for 4 hours, then end the process and let it cool naturally to room temperature.

5. A multicolor mechanoluminescent thin film based on phosphor according to claim 1, characterized in that: The polyvinyl alcohol used in step (4) is type 1788. The mass ratio of polyvinyl alcohol to deionized water in the obtained polyvinyl alcohol solution is 1:

10. Polyvinyl alcohol is slowly added to deionized water at 90°C. The concentration of the prepared polyvinyl alcohol solution is 10%. The oven conditions are to dry at 60°C for 8-10 hours to finally obtain a polyvinyl alcohol mechanoluminescent film.

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