Two-component luminescent glass as well as preparation method and application thereof

Abstract

The invention provides two-component luminescent glass as well as a preparation method and application thereof. The chemical formula of the two-component luminescent glass is (A1x1B1y1C1z1) 1-a (A2x2B2y2C2z2) a, A1 and A2 are organic cations, B1 and B2 are metal cations, C1 and C2 are halogen anions, the values of x1 and x2 are 1-3, the values of y1 and y2 are 1-2, the values of z1 and z2 are 4-9, a = 0-1, and the Tg / Tm value of A2x2B2y2C2z2 is greater than the Tg / Tm value of A1x1B1y1C1z1. According to the double-component luminescent glass, the system of a glass material is greatly expanded, the physical and chemical characteristics of the glass material can be adjusted according to actual requirements, and the double-component luminescent glass has potential application value in the optical fields of scintillators, multi-mode anti-counterfeiting, illumination, display, lasers and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent glass, and in particular relates to a two-component luminescent glass and a preparation method and application thereof. Background Art

[0002] In the field of chemistry and materials science, glass materials have attracted much attention. Compared with the long-range order of the structure of crystalline materials, the atoms, ions or molecules inside the glass are arranged in a disordered manner, and have the structural characteristics of short-range order and long-range disorder. Traditional melt-quenched glass is divided into three categories: the first is inorganic non-metallic glass, which is mainly composed of silicates, etc., has excellent optical transparency and thermal stability, and is the most important commercial glass. However, inorganic non-metallic glass is difficult to prepare and needs to be processed and formed at a high temperature greater than 800°C. The second is organic glass, which is made of polymethyl methacrylate through monomer polymerization. It has the advantages of high transparency and easy processing, but its thermal stability and chemical stability are poor, and its functionality is single, making it difficult to flexibly regulate the structure-performance relationship. The third is metallic glass, which combines the characteristics of metal and glass, has high strength and high toughness, and is used in cutting-edge fields such as military industry and high-performance aircraft engines, but it also faces challenges such as high cost, complex preparation process, and size restrictions. In recent years, the fourth type of organic-inorganic hybrid glass has attracted widespread attention. Combining the advantages of organic and inorganic components, it is expected to break the limitations of traditional melt-quenched glass and expand the structural and chemical diversity of glass.

[0003] Metal-organic framework glass, as a typical representative of organic-inorganic hybrid glass, has outstanding advantages in applications such as energy catalysis, gas adsorption, and photoelectric sensing. However, the vitrification process of metal-organic framework crystals usually requires inert atmosphere protection, and it is easy to decompose before forming a melt, which limits the preparation of this type of organic-inorganic hybrid glass. Organic-inorganic hybrid metal halide (OIMH) glass, as an emerging type of organic-inorganic hybrid glass, has been reported to be used in lighting, display, multimodal anti-counterfeiting, scintillators, photoelectric sensing and other fields due to its advantages such as low melting point, rich chemical composition, and high luminescence efficiency. The general structural formula of OIMH material is ABC, where A is an organic cation, B is a metal cation, and C is a halogen anion (Cl - Br - ,I - ). For OIMH materials, the A-site organic component and the metal-halogen component (BC) are connected by weak electrostatic interaction. Compared with the higher melting point (greater than 300°C) caused by the strong coordination bonds in metal-organic framework materials, the melting point of OIMH materials is usually lower than 250°C, and no special atmosphere protection is required, which makes it a promising glass material.

[0004] However, the current material system of OIMH glass is very limited. On the one hand, for most meltable materials, such as imidazole, pyridine, quaternary ammonium, and quaternary phosphonium OIMH materials, their melts are prone to crystallization during the cooling process, making it difficult to form amorphous glass. On the other hand, although some studies have used triphenyl quaternary phosphonium salts and diphenylguanidine salts to synthesize OIMH glass, the glass transition temperatures of these glasses are only slightly higher than room temperature, and there is a strong tendency to crystallize, and the environmental stability is poor. At the same time, the structure-performance relationship between the A-position organic component and the corresponding metal halide has not yet been clarified, and the glass-forming ability, luminescence efficiency and other properties of the material are difficult to control, requiring a large number of experimental experiments. Therefore, it is necessary to develop a new type of OIMH luminescent glass, which should be easy to prepare, have high production efficiency, and easy to control physical and chemical properties. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a two-component luminescent glass with high transparency, simple preparation process and adjustable physical and chemical properties, so that it can improve the glass forming ability and stability of a single-component material melt.

[0006] In order to solve the above technical problems, the present invention provides a two-component luminescent glass, the chemical formula of which is (A1 x1 B1 y1 C1 z1 ) 1-a (A2 x2 B2 y2 C2 z2 ) a , where A1 and A2 are organic cations, B1 and B2 are metal cations, C1 and C2 are halogen anions, x1 and x2 are 1 to 3, y1 and y2 are 1 to 2, z1 and z2 are 4 to 9, a = 0 to 1, A2 x2 B2 y2 C2 z2 T g / T m Value greater than A1 x1 B1 y1 C1 z1 T g / T m value.

[0007] Preferably, the organic cation includes at least one of an imidazole organic cation, a pyridine organic cation, a guanidine organic cation, a quaternary ammonium organic cation, and a quaternary phosphonium organic cation.

[0008] Preferably, the element of the metal cation includes at least one of lead, antimony, copper, manganese, zinc, cobalt, nickel, indium, tin and bismuth.

[0009] Preferably, the halogen anion comprises Cl - Br - ,I - At least one of .

[0010] The present invention also provides a method for preparing the two-component luminescent glass, comprising the following steps:

[0011] S1: According to the chemical formula, prepare the first component A1 x1 B1 y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 ;

[0012] S2: According to a certain ratio, the first component A1 x1 B1 y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 Mix evenly;

[0013] S3: heating the mixture at 200° C. into a molten liquid until no bubbles are generated;

[0014] S4: cooling the molten liquid and solidifying it to obtain the two-component luminescent glass;

[0015] Preferably, the A1 and A2 organic cations include at least one of imidazoles, pyridines, guanidines, quaternary ammoniums, and quaternary phosphoniums.

[0016] Preferably, the element of the metal cation includes at least one of lead, antimony, copper, manganese, zinc, cobalt, nickel, indium, tin and bismuth.

[0017] Preferably, the C1 and C2 halogen anions include Cl - Br - ,I - At least one of .

[0018] Preferably, the second component A2 x2 B2 y2 C2 z2 T g / T m The value is greater than the first component A1 x1 B1 y1 C1 z1 T g / T m value.

[0019] Preferably, the first component A1 x1 B1y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 The preparation methods include solvent evaporation method and melt crystallization method.

[0020] Preferably, the solvent volatilization method comprises: dissolving the raw material in an organic solvent at a temperature of 20-100° C. for a time of 1 to 48 hours.

[0021] Preferably, the melt crystallization method does not require the use of an organic solvent, the temperature is 50-220° C., and the time is 1 to 24 hours.

[0022] The application of the two-component luminescent glass in the preparation of luminescent materials is also within the protection scope of the present invention, and the specific steps are as follows:

[0023] S1: The first component A1 x1 B1 y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 The mixture was heated until completely melted and then cooled to room temperature.

[0024] S2: The prepared two-component luminescent glass is further applied to the fields of scintillators, multimodal anti-counterfeiting, lighting, display, lasers, etc.

[0025] Compared with the prior art, the present invention has at least the following beneficial effects:

[0026] Most of the meltable organic-inorganic hybrid metal halides, including imidazoles, pyridines, guanidines, quaternary ammoniums, quaternary phosphoniums and other metal halide materials, are prone to melt recrystallization during the cooling process and cannot form amorphous glass. g / T m Value of A2 x2 B2 y2 C2 z2 As a second component, with another T g / T m Relatively lower value of fusible organic-inorganic hybrid metal halide material A1 x1 B1 y1 C1 z1 Uniform eutectic, flexible adjustment of A1 x1 B1 y1 C1 z1 The glass-forming ability of the melt is increased to obtain a transparent two-component luminescent glass. g (Glass transition temperature) is the temperature at which a material changes from a hard and brittle glass state to a flexible rubber state.m (Melting temperature) is the temperature at which a material changes from a solid to a liquid. g / T m The ratio of reflects the material's ability to resist crystallization during the cooling stage. g / T m The higher the ratio, the narrower the crystallization temperature range of the molten state during the cooling stage, and the easier it is to form a disordered amorphous state, indicating that the material has a stronger glass-forming ability.

[0027] The preparation method of the two-component luminescent glass of the present invention is universal, can expand the types of existing glass materials, and adjust the physical and chemical properties of the glass according to actual needs. It has potential application value in optical fields such as scintillators, multimodal anti-counterfeiting, lighting, display, lasers, etc.

[0028] The preparation method of the dual-component luminescent glass of the present invention does not require expensive equipment and complex process control, the reaction conditions are not harsh, the raw materials are easily available, the production cost is low, and it is easy to industrialize. At the same time, the excellent formability of the amorphous material allows it to be processed into a variety of shapes to meet the needs of different application fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of the preparation process of two-component luminescent glass.

[0030] Figure 2 These are the results of thermogravimetric analysis and differential scanning calorimetry analysis of (TPG)2MnBr4 crystals.

[0031] Figure 3 Yes (EPy2MnBr4) 0.5 (TPG2MnBr4) 0.5 Two-component glass, (EmIm2MnBr4) 0.5 (TPG2MnBr4) 0.5 Two-component glass, (TBP2MnBr4) 0.5 (TPG2MnBr4) 0.5 Actual picture of two-component glass.

[0032] Figure 4 These are the results of thermogravimetric analysis and differential scanning calorimetry analysis of (EPy)2MnBr4 crystals, (EmIm)2MnBr4 crystals, and (TBP)2MnBr4 crystals.

[0033] Figure 5 The results of thermogravimetric and differential scanning calorimetric analysis of (DPG)2MnBr4 crystals and (PTP)2MnBr4 crystals, as well as (PTP2MnBr4) 0.5 (TPG2MnBr4) 0.5、(DPG2MnBr4) 0.5 (TPG2MnBr4) 0.5 Actual picture of two-component glass.

[0034] Figure 6 Yes (Bzmim2SbCl5) 0.5 (ETP2SbCl5) 0.5 Physical picture of two-component glass and (Bzmim)2SbCl5, (ETP)2SbCl5, (Bzmim2SbCl5) 0.5 (ETP2SbCl5) 0.5 Differential scanning calorimetry analysis results.

[0035] Figure 7 Yes (BPy2PbBr4) 0.5 (ETP2PbBr4) 0.5 Physical picture of two-component glass and (BPy)2PbBr4, (ETP)2PbBr4, (BPy2PbBr4) 0.5 (ETP2PbBr4) 0.5 The results of differential scanning calorimetry analysis.

[0036] Figure 8 Yes (PTP2MnBr4) 1-a (TPG2MnBr4) a Differential scanning calorimetry analysis results of two-component glasses.

[0037] Fig. 9 Yes (PTP2MnBr4) 1-a (TPG2MnBr4) a Transmittance, light yield and PXRD pattern of two-component glass after heat treatment. DETAILED DESCRIPTION

[0038] In order to better illustrate the purpose, technical scheme and advantages of the present invention, the concept of the present invention and the technical effects produced will be clearly and completely described below in combination with the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. The described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0039] In the description of the present invention, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0040] Unless otherwise specified, "room temperature" in the present invention means 25°C±5°C.

[0041] Unless otherwise specified, "about" in the present invention means that the allowable error is within ±2%.

[0042] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0043] Example 1

[0044] A two-component luminescent glass, the raw materials for preparing the glass include a first component A1 x1 B1 y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 ;

[0045] The first component A1 x1 B1 y1 C1 z1 For (EPy)2MnBr4 crystal, T g / T m is 0.64; the second component A2 x2 B2 y2 C2 z2 is (TPG)2MnBr4 glass, T g / T m is 0.80.

[0046] The chemical formula of the two-component luminescent glass is (A1 x1 B1 y1 C1 z1 ) 1-a (A2 x2 B2 y2 C2 z2 ) a , where a=0.5.

[0047] The preparation method of the first component (EPy)2MnBr4 crystal is as follows: 1-ethylpyridinium bromide (EPy-HBr, CAS: 1906-79-2) and manganese bromide hydrate (CAS: 10031-20-6) are mixed in a molar mass ratio of 2:1, and then placed in a muffle furnace at 200°C for calcination until the raw materials are completely melted. The melt is then cooled to room temperature to obtain (EPy)2MnBr4 crystals.

[0048] The preparation method of the second component (TPG)2MnBr4 glass is as follows: triphenylguanidine bromide and manganese bromide hydrate (CAS: 10031-20-6) are ground and mixed evenly according to a molar mass ratio of 2:1, and then placed in a muffle furnace at 220°C for firing to completely melt the raw materials. The melt is then cooled to room temperature to obtain (TPG)2MnBr4 glass.

[0049] Triphenylguanidine bromide is homemade, and the preparation method is as follows: 1,2,3-triphenylguanidine (TPG, CAS: 101-01-9) is dissolved in an appropriate amount of methanol / hydrobromic acid mixed solution, and slowly evaporated for 6 hours to obtain triphenylguanidine bromide crystals.

[0050] Reference for the preparation method of two-component luminescent glass Figure 1 As shown, specifically: the first component (EPy) 2MnBr4 crystal and the second component (TPG) 2MnBr4 glass are mixed in a mass ratio of 1:1, and placed in a muffle furnace at 200°C for firing to completely melt the raw materials. The melt is then cooled to room temperature to obtain a transparent two-component luminescent glass.

[0051] It should be noted that whether (TPG)2MnBr4 crystal or (TPG)2MnBr4 glass is used, two-component glass can be obtained, which has no effect on the final result.

[0052] The preparation method of (TPG)2MnBr4 crystals is as follows: triphenylguanidine bromide and manganese bromide (CAS: 13446-03-2) are mixed in anhydrous ethanol solution at a molar mass ratio of 2:1, heated and stirred for 30 minutes to obtain a clear precursor solution. The solution is slowly evaporated for 2 days to obtain (TPG)2MnBr4 crystals.

[0053] Figure 2 The results of thermogravimetric analysis and differential scanning calorimetry analysis of (TPG)2MnBr4 crystals are shown in Figure 2. The heating rate is 10°C / min. The T of the second component (TPG)2MnBr4 is g =72.6℃, T m =158.0℃, T g / T m It is 0.80, and has excellent glass forming ability. Figure 3 A in (EPy2MnBr4)0.5 (TPG2MnBr4) 0.5 Actual picture of two-component glass.

[0054] Example 2

[0055] This embodiment provides a two-component luminescent glass, which is prepared by referring to the method of embodiment 1. The difference from embodiment 1 is that the first component (EPy)2MnBr4 crystal is replaced by (EmIm)2MnBr4 crystal. g / T m It is 0.67.

[0056] The first component (TBP) 2MnBr4 crystal is prepared by referring to the method of Example 1, except that (EPy-HBr, CAS: 1906-79-2) is replaced by 1,2-dimethyl-3-ethylimidazolium bromide (EmIm-HBr, CAS: 98892-76-3).

[0057] Figure 3 The B in this is (EmIm2MnBr4) 0.5 (TPG2MnBr4) 0.5 Actual picture of two-component glass.

[0058] Example 3

[0059] This embodiment provides a two-component luminescent glass, which is prepared by referring to the method of embodiment 1. The difference from embodiment 1 is that the first component (EPy)2MnBr4 crystal is replaced by (TBP)2MnBr4 crystal. g / T m is 0.70.

[0060] The first component (TBP) 2MnBr4 crystal is prepared by referring to the method of Example 1, except that (EPy-HBr, CAS: 1906-79-2) is replaced by tetrabutylphosphine bromide (TBP-HBr, CAS: 3115-68-2).

[0061] Figure 3 The C in is (TBP2MnBr4) 0.5 (TPG2MnBr4) 0.5 Actual picture of two-component glass.

[0062] The glass forming ability of the first component (EPy)2MnBr4, (EmIm)2MnBr4, (TBP)2MnBr4 crystals in Examples 1 to 3 is relatively poor. Figure 4As shown in the figure, the results of differential scanning calorimetry show that the first component crystal has an obvious crystal melting peak in the second heating process, indicating that the melt undergoes crystallization during the first cooling process. After the introduction of (TPG)2MnBr4 glass with high glass forming ability, transparent two-component glass materials can be formed. This shows that this method has wide applicability and is applicable to a variety of molten materials.

[0063] Example 4

[0064] This embodiment provides a two-component luminescent glass, which is prepared by referring to the method of embodiment 1. The difference from embodiment 1 is that the first component (EPy)2MnBr4 crystal is replaced by (DPG)2MnBr4 glass. The T g / T m It is 0.71.

[0065] The preparation method of the first component (DPG) 2MnBr4 glass is as follows: diphenylguanidine hydrobromide (DPG-HBr, CAS: 93982-96-8) and manganese bromide hydrate (CAS: 10031-20-6) are reacted at a molar mass ratio of 2:1, and the mixture is fired in a muffle furnace at 200°C to obtain a molten liquid, and the melt is cooled to room temperature to obtain (DPG) 2MnBr4 glass.

[0066] During the cooling process, the melt was continuously stirred with a glass rod to obtain (DPG)2MnBr4 crystals. Figure 5 A in the figure is the test results of thermogravimetric analysis and differential scanning calorimetry of (DPG)2MnBr4 crystal. The melt forms amorphous glass during natural cooling. g It is 35.5℃.

[0067] Figure 5 B in (DPG2MnBr4) 0.5 (TPG2MnBr4) 0.5 Actual picture of two-component glass.

[0068] Example 5

[0069] This embodiment provides a two-component luminescent glass, which is prepared by referring to the method of embodiment 1. The difference from embodiment 1 is that the first component (EPy)2MnBr4 crystal is replaced by (PTP)2MnBr4 crystal. The T g / T m It is 0.71.

[0070] The first component (PTP) 2MnBr4 glass is prepared by referring to the method of Example 4, except that diphenylguanidine hydrobromide (DPG-HBr, CAS: 93982-96-8) is replaced by propyltriphenylphosphine bromide (PTP-HBr, CAS: 15912-75-1).

[0071] Figure 5 C is the test result of differential scanning calorimetry. The first component (PTP) 2MnBr4 melt does not crystallize during the cooling process and solidifies into glass. g It is 47.0℃.

[0072] Figure 5 D in is (PTP2MnBr4) 0.5 (TPG2MnBr4) 0.5 Actual picture of two-component glass.

[0073] Example 6

[0074] This embodiment provides a two-component luminescent glass, which is prepared by referring to the method of Example 1. The difference from Example 1 is that the first component (EPy)2MnBr4 crystal is replaced by (Bzmim)2SbCl5 glass; the second component (TPG)2MnBr4 glass is replaced by (ETP)2SbCl5 glass.

[0075] The preparation method of the first component (Bzmim) 2SbCl5 glass and the second component (ETP) 2SbCl5 glass is prepared by referring to the method of Example 4, and the difference from Example 4 is that diphenylguanidine hydrobromide (DPG-HBr, CAS: 93982-96-8) is replaced by 1-benzyl-3-methylimidazolium chloride (Bzmim-HCl, CAS: 36443-80-8) or ethyltriphenylphosphine chloride (ETP-HBr, CAS: 896-33-3); manganese bromide hydrate (CAS: 10031-20-6) is replaced by antimony chloride (CAS: 10025-91-9).

[0076] Figure 6 Yes (Bzmim2SbCl5) 0.5 (ETP2SbCl5) 0.5 Actual picture of two-component glass and differential scanning calorimetry test results. T g is 34.0℃, which is located at the T of the first component and the second component materials. g The intermediate value indicates the formation of two-component glass and can achieve the purpose of regulating the glass forming ability.

[0077] Example 7

[0078] This embodiment provides a two-component luminescent glass, which is prepared by referring to the method of Example 1. The difference from Example 1 is that the first component (EPy)2MnBr4 crystal is replaced by (BPy)2PbBr4 glass; the second component (TPG)2MnBr4 glass is replaced by (ETP)2PbBr4 glass.

[0079] The preparation method of the first component (BPy)2PbBr4 glass and the second component (ETP)2PbBr4 glass is prepared by referring to the method of Example 4, and the difference from Example 4 is that diphenylguanidine hydrobromide (DPG-HBr, CAS: 93982-96-8) is replaced by butylpyridinium bromide (BPy-HBr, CAS: 874-80-6) or ethyltriphenylphosphine bromide (ETP-HBr, CAS: 1530-32-1); manganese bromide hydrate (CAS: 10031-20-6) is replaced by lead bromide (CAS: 10031-22-8).

[0080] Figure 7 Yes (BPy2PbBr4) 0.5 (ETP2PbBr4) 0.5 Actual picture of two-component glass and differential scanning calorimetry test results. T g is 37.9°C, which is located at the T of the first component and the second component materials. g The intermediate value indicates the formation of two-component glass and can achieve the purpose of regulating the glass forming ability.

[0081] Example 8

[0082] Further, according to the method of Example 5, (PTP)2MnBr4 and (TPG)2MnBr4 glasses were mixed and melted in a mass ratio of 0:1, 3:7, 1:1, 7:3, 1:0 (a=1.0, 0.7, 0.5, 0.3, 0.0) to synthesize a series of (PTP2MnBr4) 1-a (TPG2MnBr4) a Two-component glass. Figure 8 As shown, the obtained two-component glasses all have only one glass transition temperature, and have a strong linear dependence on the mixing mass ratio, indicating that the glass-forming ability of the glass material can be flexibly adjusted.

[0083] Further, according to the method of Example 5, (PTP)2MnBr4 crystals and (TPG)2MnBr4 crystals were mixed in a mass ratio of 9:1, 19:1, 39:1, 59:1, 79:1, 99:1 (a = 0.100, 0.050, 0.025, 0.017, 0.0125, 0.010) to synthesize a series of (PTP2MnBr4)1-a (TPG2MnBr4) a Two-component glass. After the obtained two-component glass was placed in a 55°C oven for 24 hours, significant differences in properties occurred between the glasses. Fig. 9 As shown, the test found that the two-component glasses with a mass mixing ratio of 9:1 and 19:1 were still amorphous, while the two-component glasses with a mass mixing ratio of 39:1, 59:1, 79:1, and 99:1 had a significantly improved light yield while maintaining transparency. The powder X-ray diffraction pattern proved the precipitation of (PTP)2MnBr4 crystals, indicating that the glass forming ability and recrystallization behavior of the material can be regulated by adjusting the mixing ratio of the two-component glass.

[0084] It should be noted that most of the meltable organic-inorganic hybrid metal halides, including imidazoles, pyridines, guanidines, quaternary ammoniums, quaternary phosphoniums and other organic-inorganic hybrid metal halide materials, are prone to melt recrystallization during cooling and cannot form amorphous glass. The preparation method of the present invention effectively improves the anti-crystallization ability of the mixed melt by introducing an organic-inorganic hybrid metal halide with high glass-forming ability as the second component, inhibits the recrystallization of another component, and then forms an amorphous glass state. The method is universal and scalable.

[0085] It should also be noted that for single-component organic-inorganic hybrid metal halide materials, their glass forming ability cannot be adjusted. For example, triphenyl quaternary phosphonium metal halide glass has a glass transition temperature slightly higher than room temperature, is easy to crystallize, and has poor environmental stability. The preparation method proposed in the present invention, through co-melting with a second component (an organic-inorganic hybrid metal halide with high glass forming ability), the glass forming ability of the formed two-component melt can be adjusted by adjusting the mixing ratio, and according to actual needs, a high-stability glass and a microcrystalline glass material with high luminous efficiency can be obtained.

[0086] The present invention has been described in detail above in conjunction with the embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. A two-component luminescent glass, characterized in that: The chemical formula is (A1 x1 B1 y1 C1 z1 ) 1-a (A2 x2 B2 y2 C2 z2 ) a , where A1 and A2 are organic cations, B1 and B2 are metal cations, C1 and C2 are halogen anions, x1 and x2 are 1 to 3, y1 and y2 are 1 to 2, z1 and z2 are 4 to 9, a = 0 to 1, A2 x2 B2 y2 C2 z2 T g / T m Value greater than A1 x1 B1 y1 C1 z1 T g / T m value.

2. The two-component luminescent glass according to claim 1, characterized in that: The organic cation includes at least one of an imidazole organic cation, a pyridine organic cation, a guanidine organic cation, a quaternary ammonium organic cation and a quaternary phosphonium organic cation.

3. The two-component luminescent glass according to claim 1, characterized in that: The element of the metal cation includes at least one of lead, antimony, copper, manganese, zinc, cobalt, nickel, indium, tin and bismuth.

4. The two-component luminescent glass according to claim 1, characterized in that: The halogen anions include Cl - Br - ,I - At least one of .

5. A method for preparing the two-component luminescent glass according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1: According to the chemical formula, prepare the first component A1 x1 B1 y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 ; S2: According to the proportion, the first component A1 x1 B1 y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 After mixing, the two-component luminescent glass is obtained through melting and cooling processes; The second component A2 x2 B2 y2 C2 z2 T g / T m The value is greater than the first component A1 x1 B1 y1 C1 z1 T g / T m value.

6. The method according to claim 5, characterized in that The first component A1 x1 B1 y1 C1 z1 and the second component A2 x2 B2 y2 C2 z2 The preparation methods include solvent evaporation method and melt crystallization method.

7. The method according to claim 5, characterized in that The first component A1 x1 B1 y1 C1 z1 The invention comprises at least one of imidazole, pyridine, guanidine, quaternary ammonium and quaternary phosphonium organic-inorganic hybrid metal halides.

8. The method according to claim 5, characterized in that The second component A2 x2 B2 y2 C2 z2 The invention comprises at least one of imidazole, pyridine, guanidine, quaternary ammonium and quaternary phosphonium organic-inorganic hybrid metal halides.

9. The method according to claim 5, characterized in that The second component A2 x2 B2 y2 C2 z2 T g / T m The value is greater than 2 / 3.

10. Use of the two-component luminescent glass according to any one of claims 1 to 4 in scintillators, multimodal anti-counterfeiting, lighting, display and lasers.

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