CN114316954B - Metal sulfide oxide without activation ion electroluminescence and its preparation method and application - Google Patents

Abstract

The invention relates to a metal sulfur oxide free of activation ion electroluminescence and its preparation method and application. According to the molar ratio of Ca, Ba, Zn and S, the calcium oxide compound, the sulfur zinc compound and the barium oxide compound are mixed respectively, and then the grinding aid ethanol is added. After grinding and mixing evenly, it is dried, sintered, cooled and ground to obtain Activated ionic electroluminescent metal oxysulfides. The metal sulfur oxide of the present invention can be effectively excited by ultraviolet light, has a wide excitation band, has strong absorption in the range of 220-300nm, and has a certain phosphorescence phenomenon; except for photoluminescence and phosphorescence, the metal sulfur oxide of the present invention exhibited bright mechanoluminescence without activation by transition metal or rare earth ions.

Description

Metal sulfide oxide without activation ion electroluminescence and its preparation method and application

technical field

The invention relates to a metal sulfur oxide free of activation ion electroluminescence and a preparation method thereof, belonging to the technical field of preparation of luminescent materials.

Background technique

Mechanoluminescence (ML) is a luminescent radiation phenomenon produced by materials stimulated by a certain stress, and is a form of direct conversion of mechanical energy into light energy. Mechanoluminescent materials have potential application prospects in many fields such as artificial intelligence skin, structural health diagnosis, mechanically driven luminescence, and stress sensors, which have attracted widespread attention from researchers at home and abroad. Elastic stress luminescence has become a research and development hotspot because its radiation intensity is proportional to the size of the pressure and has outstanding advantages in practical applications. Researchers have developed a variety of elastic electroluminescent materials. Among them, metal sulfide materials are low in cost, stable in luminescence performance, and easy to manufacture. They can emit light signals only under the action of a certain force.

Researchers have developed a variety of metal sulfide elastic electroluminescent materials, such as ZnS:Mn ²⁺ , CaZnOS:Eu ³⁺ , SrZnOS:Pr ³⁺ and so on. Such materials usually obtain mechanoluminescent radiation by doping active ions such as transition metal or rare earth ions in the metal oxysulfide host. CN113214823A discloses a ternary metal sulfide with long afterglow and mechanoluminescence and its preparation method; CN111909689A discloses a mechanoluminescence composite material and its preparation method and application; CN107298977A discloses a visible-near Infrared ultra-wide dual-mode response mechanoluminescence material and preparation method thereof.

At present, under the condition of not introducing activating particles, it is difficult to realize the mechanoluminescence phenomenon visible to the naked eye only by relying on the main structure of oxysulfide, and there are few reports on metal oxysulfide elastic meroluminescent materials free of activating ions.

Contents of the invention

Aiming at the deficiencies of the prior art, especially the lack of high-efficiency host-structure luminescent materials free of active ions, the present invention provides a metal sulfide oxide free of active ions electroluminescence and a preparation method thereof. The metal oxysulfide of the present invention can be effectively excited by ultraviolet light, has a wide excitation band, and has strong absorption in the range of 220-300nm. phosphorescence and mechanoluminescence visible to the naked eye.

Technical scheme of the present invention is as follows:

A kind of metal sulfide oxide without activation ion electroluminescence, the general formula is Ca _1-x Ba _x ZnOS, 0<x<1.

Preferably according to the present invention, the metal oxysulfide is composed of CaZnOS crystal and BaZnOS crystal, the CaZnOS crystal belongs to the P63mc space point group and the hexagonal crystal system, and the BaZnOS crystal belongs to the Cmcm space point group and the orthorhombic crystal system.

According to the present invention, preferably, the general formula of the electroluminescent metal sulfide free from activation ions is 0.04≤x≤0.8. According to the present invention, preferably, the metal oxysulfide free from activation ion electroluminescence has the following chemical formula:

Ca _0.96 Ba _0.04 ZnOS, Ca _0.92 Ba _0.08 ZnOS, Ca _0.88 Ba _0.12 ZnOS, Ca _0.84 Ba _0.16 ZnOS, Ca _0.8 Ba _0.2 ZnOS, Ca _0.75 Ba _0.25 ZnOS, Ca _0.5 Ba _0.5 ZnOS, _{Ca 0.2}

According to the present invention, the preparation method of the above-mentioned metal oxysulfide free of activation ion electroluminescence comprises the steps of:

Weigh calcium oxide compound, sulfur zinc compound and barium oxide compound according to the molar ratio of Ca, Ba, Zn and S respectively, add grinding aid ethanol after mixing, grind and mix evenly, then dry, sinter, cool and grind That is, the metal oxysulfide is free from activation ion electroluminescence.

According to the present invention, preferably, the calcium oxide compound is calcium carbonate or calcium oxide;

Preferably, the sulfur-zinc compound is zinc sulfide;

Preferably, the barium oxide compound is barium carbonate or barium oxide.

According to the present invention, calcium oxide compound, barium oxide compound and sulfur zinc compound are respectively weighed according to Ca:Ba:Zn:S=1-x:x:1:1.

According to the present invention, preferably, the volume ratio of the total mass of raw materials to ethanol is 1:0.5-2. The total mass of the raw materials is the total mass of calcium carbonate, zinc sulfide and barium carbonate.

According to the present invention, preferably, before sintering, it is ground to a particle size of less than or equal to 0.15 mm.

According to the present invention, preferably, the drying temperature is 60-80° C., and the drying time is 1-3 hours.

According to the present invention, preferably, the sintering temperature is 1200-1400K, and the sintering time is 3-5h; preferably, the sintering temperature is 1275K, and the sintering time is 4h; the crystallization is not complete if the sintering temperature is too low, and the temperature is too high. The tube furnace has high requirements and high risk of experiment;

Preferably, the sintering atmosphere is an oxygen-free atmosphere, more preferably Ar gas.

According to the present invention, preferably, after sintering and cooling, it is ground to a particle size of less than or equal to 0.155 mm.

The present invention also provides a method for preparing a metal sulfide block solid without activation ion electroluminescence, comprising the following steps:

The polydimethylsiloxane, the metal sulfide and the curing agent are evenly mixed, and the bubbles are removed and solidified to obtain the metal sulfide block solid without activation ion electroluminescence.

According to the present invention, preferably, the curing agent is a silane coupling agent. The silane coupling agent can be vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane and the like.

According to the present invention, preferably, the mass ratio of described polydimethylsiloxane and metal oxysulfide is 4-6:1, preferably 5:1; The mass ratio of described polydimethylsiloxane and curing agent The mass ratio is 8-12:1, preferably 10:1.

According to the present invention, air bubbles are removed by vacuuming.

According to the present invention, preferably, the curing temperature is 70-90°C, preferably 80°C. The curing time is 1-3h, preferably 2h.

The present invention also provides the application of the metal sulfide oxide free of activation ion electroluminescence in the field of electroluminescence.

Technical characteristics and beneficial effects of the present invention:

1. The metal sulfide oxide without activation ion electroluminescence of the present invention can be effectively excited by ultraviolet light without activation ion, has a relatively wide excitation band, and has strong absorption in the range of 220-300 nm.

2. In addition to photoluminescence and phosphorescence, the metal sulfide oxide of the present invention has a highly sensitive and non-destructive mechanoluminescence phenomenon that does not need to be activated by ultraviolet light, and can emit light only in the presence of pressure. No pre-irradiation and other treatments are required. The metal sulfide oxide of the invention can detect strong luminescence phenomenon under low pressure, which is beneficial to its application in the field of high-sensitivity luminescence.

3. The metal sulfide oxide without activation ion electroluminescence of the present invention can observe a certain amount of phosphorescence when the excitation source at 365 nm is turned off, and the luminescence spectrum can be detected within 160 s.

4. The metal sulfide oxide without activation ion electroluminescence of the present invention has a stable structure, a simple synthesis method, and is convenient for large-scale production.

5. The preparation process of the present invention is simple, and a block material with high crystallinity can be obtained without using a flux.

Description of drawings

Fig. 1 is the comparison diagram of the X-ray powder diffraction spectrum and the standard diffraction card diagram of the metal oxysulfide sample which is free from activation ion electroluminescence produced by the proportions (1)-(8) of Example 1.

Fig. 2 is the scanning electron microscope image and the EDS energy spectrum image of the metal oxysulfide sample which is free from activation ion electroluminescence produced in the proportion (4) of Example 1.

Fig. 3 is the diffuse reflectance analysis diagram of the metal sulfide sample without activation ion electroluminescence luminescence obtained in the proportioning ratio (1)-(8) of Example 1.

Fig. 4 is the fluorescence emission spectrum of the metal oxysulfide sample without activation ion electroluminescence produced in the proportions (1)-(8) of Example 1, and the excitation wavelength is 365nm.

Fig. 5 is the fluorescence lifetime spectrum of the metal sulfide sample without activation ion electroluminescence produced in the proportion (4) of Example 1, and the excitation wavelength is 365nm.

Fig. 6 is the phosphorescence spectrogram of the metal oxysulfide sample without activation ion electroluminescence produced by the ratio (1)-(8) of Example 1. The excitation wavelength is 365nm.

Fig. 7 is the phosphorescence decay time of 20-160s after the decay time is 20-160s after the 365nm excitation light source irradiation 10s of the metal sulfide oxide sample that is free of activation ion electroluminescence that the proportioning (1)-(8) of embodiment 1 makes picture.

Fig. 8 is the mechanoluminescence spectrum of the bulk solid sample of metal oxysulfide free from activation ion electroluminescence produced in the ratios (1)-(8) of Example 2 under the same pressure.

Fig. 9 is the fluorescence emission spectrum of the metal oxysulfide sample prepared in Comparative Example 1-2, the excitation wavelength is 365nm.

Fig. 10 is the fluorescence emission spectrum of the metal oxysulfide sample prepared in Comparative Example 3-4, the excitation wavelength is 365nm.

Fig. 11 is the fluorescence emission spectrum of the metal oxysulfide sample prepared in Comparative Example 5, and the excitation wavelength is 365nm.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but not limited thereto.

At the same time, the experimental methods described in the following examples, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.

Example 1

A kind of preparation method of metal oxysulfide free from activation ion electroluminescence, the steps are as follows:

Choose calcium carbonate, zinc sulfide, and barium carbonate as the starting compound raw materials, and take four kinds of compound raw materials respectively according to the stoichiometric ratio of the following elements, totally 10 groups, and the proportioning ratio is as follows:

(1) Ca:Ba:Zn:S=1:0:1:1, corresponding to x=0; the obtained metal oxysulfide is abbreviated as CaZnOS;

(2) Ca:Ba:Zn:S=1:0.04:1:1, corresponding to x=0.04; the obtained metal oxysulfide is abbreviated as Ca _0.96 Ba _0.04 ZnOS;

(3) Ca:Ba:Zn:S=1:0.08:1:1, corresponding to x=0.08; the obtained metal oxysulfide is abbreviated as Ca _0.92 Ba _0.08 ZnOS;

(4) Ca:Ba:Zn:S=1:0.12:1:1, corresponding to x=0.12; the obtained metal oxysulfide is abbreviated as Ca _0.88 Ba _0.12 ZnOS;

(5) Ca:Ba:Zn:S=1:0.16:1:1, corresponding to x=0.16; the obtained metal oxysulfide is abbreviated as Ca _0.84 Ba _0.16 ZnOS;

(6) Ca:Ba:Zn:S=1:0.2:1:1, corresponding to x=0.2; the obtained metal oxysulfide is abbreviated as Ca _0.8 Ba _0.2 ZnOS;

(7) Ca:Ba:Zn:S=1:0.25:1:1, corresponding to x=0.25; the obtained metal oxysulfide is abbreviated as Ca _0.75 Ba _0.25 ZnOS;

(8) Ca:Ba:Zn:S=1:0.5:1:1, corresponding to x=0.5; the obtained metal oxysulfide is abbreviated as Ca _0.5 Ba _0.5 ZnOS;

(9) Ca:Ba:Zn:S=1:0.8:1:1, corresponding to x=0.8; the obtained metal oxysulfide is abbreviated as Ca _0.2 Ba _0.8 ZnOS;

(10) Ca:Ba:Zn:S=0:1:1:1, corresponding to x=1; the obtained metal oxysulfide is abbreviated as BaZnOS;

Above-mentioned raw material is mixed, add ethanol as grinding aid (the volume ratio of raw material gross mass and ethanol is 1:1, and the gross mass of described raw material is calcium carbonate, zinc sulfide, the gross mass of barium carbonate), grind and mix to The particle size of the raw material is less than or equal to 0.15mm, put it into a quartz crucible, and dry it in a 70°C oven for 2 hours; put the quartz crucible in a corundum boat, and put it into a horizontal high-temperature tube furnace. Strictly control the heating rate (heating rate 10°C/min), calcinate at 1275K for 4 hours, the atmosphere is Ar gas, cool to room temperature, and grind until the particle size is less than or equal to 0.355mm. .

Fig. 1 is the metal oxysulfide sample of the free activation ion electroluminescence that embodiment 1 proportioning (1)-(8) makes, and the X-ray powder diffraction spectrum and the standard diffraction card of the sample that comparative example 1-2 prepares Comparison chart of the graph. The German Bruker AXS D8 Advance diffractometer is used, the radiation source is Cu target, the test voltage is 40kV, the test current is 40mA, the scan step is 0.02°/step, and the scan speed is 0.12s/step. Among them, the XRD pattern analysis shows that the sample diffraction peak obtained at 1275K can coincide with the CaZnOS and BaZnOS standard diffraction card diagrams, that is, the prepared metal oxysulfide is composed of CaZnOS crystal and BaZnOS crystal, and the CaZnOS crystal belongs to the P63mc space point group, hexagonal crystal System, BaZnOS crystal structure belongs to Cmcm space point group, hexagonal crystal system.

Fig. 2 is the scanning electron micrograph and the EDS energy spectrogram of the metal oxysulfide sample of the non-activated ion electroluminescence that is prepared in embodiment 1 proportioning (4), adopts German Carl Zeiss G300 FE-SEM System and Debrook Nano GmbHBerlin Determination. It can be seen from Figure 2 that the morphology and particle size of the ternary metal oxysulfide sample is blocky solid. The EDS energy spectrum shows that the barium element is successfully doped into the metal oxysulfide sample. The molar content of Ca, Ba, Zn, and S in the sample is similar to the feeding ratio through elemental analysis, and the molar ratio of each element in the sample is also the same. Roughly in line with the general formula (because there are errors in the elemental analysis test).

Fig. 3 is the diffuse reflectance analysis figure of the metal oxysulfide sample of the free activation ion electroluminescence that the proportioning (1)-(8) of embodiment 1 makes, as shown in the figure, the material shows 220-300nm ultraviolet excitation band, the excitation band width is wide.

Fig. 4 is the fluorescence emission spectrum of the metal oxysulfide sample that is free from activation ion electroluminescence produced by the proportioning (1)-(8) of Example 1, the excitation wavelength is 365nm, and the test instrument is Tianjin Gangdong Science and Technology Development Co., Ltd. Co., Ltd. F320 steady-state transient fluorescence spectrometer for measurement, using xenon lamp as the excitation light source, and the excitation wavelength is 365nm. As shown in Fig. 4, under excitation at 365nm, the metal sulfide oxide sample without activation ion electroluminescence produced by the ratio (1)-(8) has two fluorescence peaks, which are respectively located at about 490nm and 612nm.

Fig. 5 is the fluorescence lifetime spectrum of the metal sulfide oxide sample without activation ion electroluminescence produced in the proportion (4) of Example 1, the excitation wavelength is 365nm, the emission wavelength is 612nm, and the fluorescence lifetime is 0.7355ms.

Fig. 6 is the phosphorescence spectrogram of the metal oxysulfide sample without activation ion electroluminescence produced by the ratio (1)-(8) of Example 1. The excitation wavelength is 365nm, and only shows a strong phosphorescence spectrum around 600nm, and as the value of x increases, the position of the spectral peak shifts red, and the phosphorescence is the strongest when x=0.12.

Fig. 7 is the phosphorescence decay time of 20-160s after the decay time is 20-160s after the 365nm excitation light source irradiation 10s of the metal sulfide oxide sample that is free of activation ion electroluminescence that the proportioning (1)-(8) of embodiment 1 makes As shown in the figure, the decay time of the sample varies with the change of the x value. When x=0.08, the decay time is up to 160s, and when x=0.25, the decay time is the shortest, only 20s. The significant difference in phosphorescence decay time indicates that it is expected to be applied in the field of anti-counterfeiting.

Example 2

A method for preparing a bulk solid of metal oxysulfide free of activation ion electroluminescence, comprising the steps of:

Choose 8 groups of ternary metal sulfoxide crystals in the ratio (1)-(8) of Example 1 as raw materials, and mix them with Dow Corning 184 silicone rubber A component (the main component is polydimethylsiloxane) respectively (A The mass ratio of component and ternary metal sulfide crystal is 5:1), add Dow Corning 184 silicone rubber B component (curing agent), the weight ratio of B component to polydimethylsiloxane is 1:10, mix Evenly, vacuumize to remove air bubbles, solidify at 80°C for 2 hours, and make a solid with a preset shape.

Fig. 8 is the mechanoluminescence spectrum of the bulk solid sample of metal oxysulfide free from activation ion electroluminescence produced in the ratios (1)-(8) of Example 2 under the same pressure. When carrying out mechanoluminescence experiments in a dark room, red mechanoluminescence can be observed. Using the self-made mechanoluminescence spectrometer in the laboratory, in the dark room, under the pressure stimulation of 10N, the 8 kinds of ratios all have red mechanoluminescence, and the luminescence peak wavelength is 600nm-630nm. With the increase of x, the fluorescence peak red shifts. The mechanoluminescence is the strongest when x=0.16.

Comparative example 1

The preparation method of CaZnOS is as follows:

Choose calcium carbonate, zinc sulfide, as starting compound raw material, according to following each element stoichiometric ratio, take raw material respectively, comparative ratio is as follows:

Ca:Zn:S=1:1:1.

The above raw materials are mixed, and ethanol is added as a grinding aid (the volume ratio of the total mass of the raw materials to ethanol is 1:1, and the total mass of the raw materials is the total mass of calcium carbonate and zinc sulfide), and the mixture is uniformly ground to the particle size of the raw materials Less than or equal to 0.15mm, put it into a quartz crucible, and dry it in a 70°C oven for 2 hours; place the quartz crucible in a corundum boat and put it into a horizontal high-temperature tube furnace. Strictly control the heating rate (heating rate 10°C/min), calcinate at 1275K for 4 hours, cool to room temperature, and grind until the particle size is less than or equal to 0.355mm to obtain metal oxysulfide crystals.

The preparation method of massive solid, the steps are as follows:

The metal oxysulfide crystal prepared above is used as a raw material, and mixed with Dow Corning 184 silicone rubber A component (the main component is polydimethylsiloxane) respectively (the mass ratio of A component and ternary metal oxysulfide crystal is 5:1), add Dow Corning 184 silicone rubber component B (curing agent), the weight ratio of component B to polydimethylsiloxane is 1:10, mix well, vacuumize to remove air bubbles, and cure at 80°C for 2 hours, Made into solids of preset shapes.

Comparative example 2

The preparation method of BaZnOS is as follows:

Choose zinc sulfide, barium carbonate, according to following each element stoichiometric ratio, take by weighing above-mentioned compound raw material respectively, proportioning is as follows:

Ba:Zn:S=1:1:1;

The above raw materials are mixed, and ethanol is added as a grinding aid (the volume ratio of the total mass of the raw materials to ethanol is 1:1, and the total mass of the raw materials is the total mass of zinc sulfide and barium carbonate), and the mixture is uniformly ground to the particle size of the raw materials Less than or equal to 0.15mm, put it into a quartz crucible, and dry it in a 70°C oven for 2 hours; place the quartz crucible in a corundum boat and put it into a horizontal high-temperature tube furnace. Strictly control the heating rate (heating rate 10°C/min), calcinate at 1275K for 4 hours, cool to room temperature, and grind until the particle size is less than or equal to 0.355mm.

The BaZnOS prepared above was used as a raw material to prepare massive solids, and the preparation method was as in Comparative Example 1.

Figure 9 is the fluorescence emission spectrum of the metal oxysulfide sample prepared in Comparative Example 1-2, the excitation wavelength is 365nm, as shown in Figure 9, CaZnOS shows a weak fluorescence phenomenon, while BaZnOS shows a single fluorescence peak at around 500nm, Using the self-made mechanoluminescence spectrometer in the laboratory, neither CaZnOS nor BaZnOS was observed mechanoluminescence phenomenon when carrying out the mechanoluminescence experiment in the dark room.

Comparative example 3

The preparation method of CaZnOS under _O2 atmosphere is as follows:

Choose zinc sulfide, calcium carbonate as starting compound raw material, according to following each element stoichiometric ratio, take by weighing above-mentioned compound raw material respectively, proportioning is as follows:

Ca:Zn:S=1:1:1;

The above raw materials are mixed, and ethanol is added as a grinding aid (the volume ratio of the total mass of the raw materials to ethanol is 1:1, and the total mass of the raw materials is the total mass of zinc sulfide and calcium carbonate), and the mixture is uniformly ground to the particle size of the raw materials Less than or equal to 0.15mm, put it into a quartz crucible, and dry it in a 70°C oven for 2 hours; place the quartz crucible in a corundum boat and put it into a horizontal high-temperature tube furnace. Strictly control the heating rate (heating rate 10°C/min), calcinate at 1275K for 4 hours, cool to room temperature, and grind until the particle size is less than or equal to 0.355mm.

The CaZnOS prepared above was used as a raw material to prepare massive solids, and the preparation method was as in Comparative Example 1.

Comparative example 4

The preparation method of BaZnOS under _O2 atmosphere is as follows:

Choose zinc sulfide, calcium carbonate as starting compound raw material, according to following each element stoichiometric ratio, take by weighing above-mentioned compound raw material respectively, proportioning is as follows:

Ba:Zn:S=1:1:1;

The above raw materials are mixed, and ethanol is added as a grinding aid (the volume ratio of the total mass of the raw materials to ethanol is 1:1, and the total mass of the raw materials is the total mass of zinc sulfide and calcium carbonate), and the mixture is uniformly ground to the particle size of the raw materials Less than or equal to 0.15mm, put it into a quartz crucible, and dry it in a 70°C oven for 2 hours; place the quartz crucible in a corundum boat and put it into a horizontal high-temperature tube furnace. Strictly control the heating rate (heating rate 10°C/min), calcinate at 1275K for 4 hours, cool to room temperature, and grind until the particle size is less than or equal to 0.355mm.

The BaZnOS prepared above was used as a raw material to prepare massive solids, and the preparation method was as in Comparative Example 1.

Fig. 10 is the fluorescence emission spectrum of the metal oxysulfide sample prepared in Comparative Example 3-4, the excitation wavelength is 365nm. CaZnOS and BaZnOS calcined under O2 atmosphere only show a weak fluorescence peak around 500nm.

Comparative example 5

Ca _1-x Ba _x ZnOS under O ₂ atmosphere, where the values of x are 0.08 and 0.16, the preparation method is as follows:

Choose zinc sulfide, calcium carbonate as starting compound raw material, according to following each element stoichiometric ratio, take by weighing above-mentioned compound raw material respectively, proportioning is as follows:

Ca:Ba:Zn:S＝0.92:0.08:1:1, corresponding to x＝0.08;

Ca:Ba:Zn:S＝0.84:0.16:1:1, corresponding to x＝0.16;

The above raw materials are mixed, and ethanol is added as a grinding aid (the volume ratio of the total mass of the raw materials to ethanol is 1:1, and the total mass of the raw materials is the total mass of zinc sulfide and calcium carbonate), and the mixture is uniformly ground to the particle size of the raw materials Less than or equal to 0.15mm, put it into a quartz crucible, and dry it in a 70°C oven for 2 hours; place the quartz crucible in a corundum boat and put it into a horizontal high-temperature tube furnace. Strictly control the heating rate (heating rate 10°C/min), calcinate at 1275K for 4 hours, cool to room temperature, and grind until the particle size is less than or equal to 0.155mm.

The bulk solid was prepared by using the Ca _1-x Ba _x ZnOS prepared above under an O ₂ atmosphere as a raw material, and the preparation method was as in Comparative Example 1.

Fig. 11 is the fluorescence emission spectrum of the metal oxysulfide sample prepared in Comparative Example 5, and the excitation wavelength is 365nm. The sample only showed a weak fluorescence peak at about 500nm, and no mechanoluminescence phenomenon was observed in any sample when the mechanoluminescence experiment was carried out in a dark room using a mechanoluminescence spectrometer.

Claims (11)

1. The metal oxysulfide free from activating ionic force to cause luminescence is characterized in that the general formula of the metal oxysulfide is Ca _1-x Ba _x ZnOS， 0<x<1。

2. The activated ion-free mechanoluminescence-containing metal sulfide according to claim 1, wherein 0.04. Ltoreq. X.ltoreq.0.8 in the general formula of the activated ion-free mechanoluminescence-containing metal sulfide.

3. The active-free ionic mechanoluminescence-containing metal sulfide according to claim 1, wherein said active-free ionic mechanoluminescence-containing metal sulfide has the following chemical formula:

Ca _0.96 Ba _0.04 ZnOS、Ca _0.92 Ba _0.08 ZnOS、Ca _0.88 Ba _0.12 ZnOS、Ca _0.84 Ba _0.16 ZnOS、Ca _0.8 Ba _0.2 ZnOS、

Ca _0.75 Ba _0.25 ZnOS、Ca _0.5 Ba _0.5 ZnOS、Ca _0.2 Ba _0.8 ZnOS。

4. a method for preparing the activated ion-free mechanoluminescence-promoting metal sulfide oxide as claimed in claim 1, comprising the steps of:

respectively weighing calcium oxide, sulfur zinc compound and barium oxide according to the molar ratio of Ca, ba, zn and S, mixing, adding grinding aid ethanol, grinding, uniformly mixing, drying, sintering, cooling and grinding to obtain the metal oxysulfide free from activating ionic force luminescence, wherein the sintering atmosphere is an oxygen-free atmosphere.

5. The method according to claim 4, wherein the calcium oxide compound is calcium carbonate or calcium oxide, the zinc sulfide compound is zinc sulfide, and the barium oxide compound is barium carbonate or barium oxide.

6. The method for preparing activated ion-free mechanoluminescence-promoting metal sulfide as claimed in claim 4, wherein the volume ratio of the total mass of the calcium oxide compound, the zinc sulfide compound and the barium oxide compound to ethanol is 1.

7. The method of claim 4, wherein the method comprises one or more of the following conditions:

i. grinding the mixture to a particle size of less than or equal to 0.15mm before sintering;

ii. The drying temperature is 60-80 ℃, and the drying time is 1-3h;

and iii, sintering, cooling, and grinding until the particle size is less than or equal to 0.355mm.

8. The method for preparing activated ion-free mechanoluminescence-promoting metal sulfide as claimed in claim 4, wherein the sintering temperature is 1200 to 1400K.

9. A method for preparing a bulk solid from the activated ion-free mechanoluminescence-inducing metal sulfide oxide of claim 1, comprising the steps of:

uniformly mixing polydimethylsiloxane, ternary metal oxysulfide and a curing agent, removing bubbles, and curing to obtain a blocky solid with phosphorescence and photoluminescence;

the general formula of the ternary metal oxysulfide is Ca _1-x Ba _x ZnOS， 0<x<1。

10. The method of claim 9, wherein the method comprises one or more of the following conditions:

i. the curing agent is a silane coupling agent;

ii. The mass ratio of the polydimethylsiloxane to the ternary metal oxysulfide is 4-6:1; the mass ratio of the polydimethylsiloxane to the curing agent is 8-12;

iii, the curing temperature is 70-90 ℃, and the curing time is 1-3h.

11. The activated ion-free mechanoluminescence-containing metal sulfide according to claim 1, for use in the field of mechanoluminescence.

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