Organic-inorganic hybrid rare-earth-based halide luminescent glass material as well as preparation method and application thereof

Abstract

The invention relates to an organic-inorganic hybrid rare-earth-based halide luminescent glass material as well as a preparation method and application thereof, and belongs to the technical field of hybrid glass materials. The invention provides an organic-inorganic hybrid rare earth halide luminescent glass material, the chemical general formula of which is AxByCz, in which A is an organic cation containing imidazolyl or pyridyl; b is a rare earth metal cation, C is a halogen anion, x is equal to 3-4, y is equal to 1, and z is equal to 6-7. Organic cations containing imidazolyl or pyridyl are adopted as organic components and can react with rare earth metal ions to form corresponding metal halide crystals, and the high-brightness, uniform and transparent hybrid rare earth based halide luminescent glass can be obtained through a low-temperature melting quenching method.

Description

Technical Field

[0001] The present invention belongs to the technical field of hybrid glass materials, and particularly relates to an organic-inorganic hybrid rare earth-based halide luminescent glass material, a preparation method thereof, and applications thereof. Background Art

[0002] Compared with traditional inorganic glass, the preparation temperature of hybrid glass can be reduced to below 300 °C (the preparation temperature of traditional inorganic glass usually requires more than 1000 °C), and at the same time, it has better hardness performance and anti-aging characteristics than organic glass. The organic-inorganic hybrid glass family mainly includes: coordination polymer (CP) glass, metal-organic framework (MOF) glass, hybrid metal halide glass, and metal-organic composite glass. Among them, hybrid metal halide luminescent glass not only retains the framework connectivity and coordination mode of the crystal, but also exhibits various physical and chemical properties different from the crystal state, and has broad application prospects in photonics, magnetics, electronics, etc.

[0003] Hybrid metal halides are composed of organic cations, metal cations, and halogen ions. Metal ions and halogen ions coordinate to form metal halide polyhedra, which are isolated by organic cations and connected by weak electrostatic interactions. Therefore, they have a relatively low melting point. The preparation of hybrid metal halide glass often adopts the low-temperature melting and quenching method. However, during the melting process, the organic components will decompose when heated, making it difficult to obtain a uniform and stable melt. In addition, recrystallization problems will inevitably occur during the quenching process, resulting in challenges in the synthesis of hybrid metal halide glass. To overcome these problems, the melting temperature of the hybrid metal halide material must be lower than the decomposition temperature, and at the same time, large-size organic cations with high steric hindrance are selected to increase the melt viscosity to prevent the crystallization tendency during the quenching process. These condition limitations lead to a very limited type of hybrid metal halide glass.

[0004] Hybrid metal halide glass retains the excellent optical properties of its crystal and has attracted attention in the fields of solid-state lighting, backlight display, optical anti-counterfeiting, radiation detection, etc. However, the currently available metal luminescent centers (such as Pb 2 +、Zn2+、Sb 3 +、Cu+、Mn2+, etc.) are limited in number and have obvious limitations: 1) The emission spectrum range is limited; 2) It restricts the degree of freedom in the structural design of new materials; 3) It limits the application range of such glasses in the optoelectronic field. Lanthanide rare earth ions play a crucial role in various optoelectronic fields due to their tunable multicolor luminescence characteristics, excellent luminescence properties, and stability. However, research on the preparation, optical properties, and applications of hybrid rare earth-based halide glasses is still very scarce. Therefore, it is very meaningful to develop a preparation method for hybrid rare earth-based halide luminescent glass materials. Summary of the Invention

[0005] The object of the present invention is to overcome the problems existing in the above-mentioned prior art, and to provide an organic-inorganic hybrid rare earth-based halide luminescent glass material, a preparation method and an application thereof.

[0006] The present invention is realized by the following technical solutions:

[0007] In a first aspect, the present invention provides an organic-inorganic hybrid rare earth-based halide luminescent glass material, the chemical general formula of which is A x B y C z , wherein A is an organic cation containing an imidazole group or a pyridine group; B is a rare earth metal cation, C is a halogen anion, x = 3-4, y = 1, z = 6-7.

[0008] Preferably, the A includes at least one of 1-benzyl-3-methylimidazole and its derivatives, 1-benzyl-2-methylimidazole and its derivatives, N-benzylimidazole and its derivatives, 1-butyl-3-methylimidazole and its derivatives, 1,3-dimethylimidazole and its derivatives, 1-ethyl-2,3-dimethylimidazole and its derivatives, benzimidazole and its derivatives, N-butylpyridinium bromide and its derivatives.

[0009] Preferably, the B includes at least one of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y) cations.

[0010] Preferably, the C includes at least one of chlorine, bromine and iodine ions.

[0011] In a second aspect, the present invention provides another preparation method of the organic-inorganic hybrid rare earth-based halide luminescent glass material, heating the crystal or powder of the chemical general formula A x B y C z to melting, and then cooling to obtain the organic-inorganic hybrid rare earth-based halide luminescent glass material.

[0012] Preferably, the temperature for heating and melting is 100°C - 280°C, the time for holding the melt is 3 min - 60 min, and the time for cooling is 3 s - 300 s.

[0013] Preferably, the cooling is carried out in a protective atmosphere or an atmospheric atmosphere, and the protective atmosphere includes at least one of argon and nitrogen.

[0014] In this preparation method, the organic-inorganic hybrid rare earth-based halide luminescent glass material is obtained by first obtaining crystals or powders and then performing heat melting and rapid cooling.

[0015] In a specific embodiment of the present invention, the chemical general formula A x B y C z The preparation method of the crystal includes the following steps: Weigh the halide salts of A and the halide salts of B according to the stoichiometric ratio of the chemical general formula A x B y C z Mix and heat to melting, and cool to crystallize to obtain the crystal of the chemical general formula A x B y C z .

[0016] Thirdly, the present invention provides another preparation method of an organic-inorganic hybrid rare earth-based halide luminescent glass, including the following steps: Weigh the halide salts of A and the halide salts of B according to the stoichiometric ratio of the chemical general formula A x B y C z Mix and heat to melting, and cool to obtain the organic-inorganic hybrid rare earth-based halide luminescent glass material.

[0017] Preferably, the cooling is carried out in a protective atmosphere or an atmospheric atmosphere; more preferably, the protective atmosphere includes at least one of nitrogen and argon.

[0018] Preferably, the heating temperature is 100°C - 280°C, the melting holding time is 3 min - 60 min, and the cooling time is 3 s - 300 s.

[0019] In this preparation method, by mixing and heating the halide salts of raw materials A and B to melting and then rapidly cooling to room temperature, the organic-inorganic hybrid rare earth-based halide luminescent glass material can be directly obtained. Compared with the first method, this method can effectively reduce the preparation steps of the organic-inorganic hybrid rare earth-based halide luminescent glass and is more suitable for mass production.

[0020] Fourthly, the present invention provides the application of the organic-inorganic hybrid rare earth-based halide luminescent glass material or the organic-inorganic hybrid rare earth-based halide luminescent glass material prepared by the preparation method of the organic-inorganic hybrid rare earth-based halide luminescent glass material in the fields of X-ray detection imaging, light-emitting diodes, optical temperature measurement, luminescent anti-counterfeiting, upconversion materials, and solid-state lighting.

[0021] The organic-inorganic hybrid rare-earth-based halide luminescent glass material of the present invention has high brightness and uniform luminescence, and has broad application prospects in the fields of X-ray detection imaging, light-emitting diodes, optical temperature measurement, luminescent anti-counterfeiting, upconversion materials, solid-state lighting, etc.

[0022] The present invention has the following beneficial effects: The present invention provides a series of organic-inorganic hybrid rare-earth-based halide luminescent glasses. Using organic ligands containing imidazole groups or pyridyl groups as organic cation components, they can react with rare-earth metal ions, and high-brightness, uniform and transparent rare-earth-based halide luminescent glasses can be obtained by the low-temperature melting and quenching method. The preparation method of the organic-inorganic hybrid rare-earth-based halide luminescent glass material of the present invention is simple and efficient, and is suitable for industrial production. The obtained luminescent glass material can be applied to various fields such as X-ray detection imaging, light-emitting diodes, optical temperature measurement, luminescent anti-counterfeiting, upconversion materials, solid-state lighting, etc. Brief Description of the Drawings

[0023] Figure 1 XRD patterns of the crystal materials of Example 1 and Example 2;

[0024] Figure 2 Thermogravimetric analysis and differential scanning calorimetry curves of the glass materials of Example 1 and Example 2;

[0025] Figure 3 Luminescence images of the Bzmim3EuCl6 and Bzmim3TbCl6 glass materials prepared in Example 1 and Example 2 under 365 nm ultraviolet light;

[0026] Figure 4 Luminescence images of the glass materials prepared in Examples 3-5 under 365 nm ultraviolet light;

[0027] Figure 5 Luminescence image of the Hy3CeBr3 glass material of Example 6 under 365 nm ultraviolet light;

[0028] Figure 6 Luminescence image of the BMI3EuCl6 glass material of Example 7 under 365 nm ultraviolet light;

[0029] Figure 7 Luminescence images of the glass materials of Example 8 and Example 9 under 365 nm ultraviolet light;

[0030] Figure 8 Luminescence image of the Bzmim3CeBr6 glass material of Example 10 under 365 nm ultraviolet light;

[0031] Figure 9 Luminescence image of the MTP3CeCl6 material of Comparative Example 1 under 365 nm ultraviolet light;

[0032] Figure 10 Emission image of the HTP3CeBr6 material of Comparative Example 2 under 365 nm ultraviolet light;

[0033] Figure 11 Emission image of the TBA3TbCl6 material of Comparative Example 3 under 365 nm ultraviolet light. Detailed implementation manners

[0034] To better illustrate the objectives, technical solutions, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0035] Unless otherwise specified, the test methods used in the examples are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, can all be obtained from commercial channels.

[0036] Example 1

[0037] A preparation method of an organic-inorganic hybrid rare-earth-based halide luminescent glass material, comprising the following steps:

[0038] (1) Mix 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl) and EuCl3·6H2O in a molar ratio of 3:1, heat to 220 °C, keep warm for 20 min, and then slowly cool to 25 °C over 24 h to obtain Bzmim3EuCl6 crystals;

[0039] (2) Place the Bzmim3EuCl6 crystals obtained in step (1) in a muffle furnace, heat to 230 °C, keep warm for 20 min to obtain a uniform melt, and rapidly cool to room temperature in a nitrogen atmosphere after 180 s to obtain the organic-inorganic hybrid rare-earth-based halide luminescent glass material, the chemical general formula of which is Bzmim3EuCl6.

[0040] Example 2

[0041] This example provides an organic-inorganic hybrid rare-earth-based halide luminescent glass material Bzmim3TbCl6, which is prepared by referring to the method of Example 1. The difference from Example 1 is that EuCl3·6H2O is replaced by TbCl3·6H2O.

[0042] Example 3

[0043] This example provides an organic-inorganic hybrid rare-earth-based halide luminescent glass material Bzmim3Tb 0.75 Eu 0.25Cl6 was prepared according to the method of Example 1, and the difference from Example 1 is that the mixing of 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl) and EuCl3·6H2O in a molar ratio of 3:1 was replaced by the mixing of 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl), EuCl3·6H2O and TbCl3·6H2O in a molar ratio of 3:0.25:0.75.

[0044] Example 4

[0045] This example provides an organic-inorganic hybrid rare earth-based halide luminescent glass material Bzmim3Tb 0.5 Eu 0.5 Cl6 was prepared according to the method of Example 3, and the difference from Example 3 is that the mixing ratio of 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl), EuCl3·6H2O and TbCl3·6H2O was replaced by 3:0.5:0.5.

[0046] Example 5

[0047] This example provides an organic-inorganic hybrid rare earth-based halide luminescent glass material Bzmim3Tb 0.25 Eu 0.75 Cl6 was prepared according to the method of Example 3, and the difference from Example 3 is that the mixing ratio of 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl), EuCl3·6H2O and TbCl3·6H2O was replaced by 3:0.75:0.25.

[0048] Example 6

[0049] This example provides an organic-inorganic hybrid rare earth-based halide luminescent glass material Hy3CeBr3, which was prepared according to the method of Example 1. The difference from Example 1 is that the mixing of 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl) and EuCl3·6H2O in a molar ratio of 3:1 was replaced by the mixing of N-hexylpyridinium bromide (Hy HBr) and CeBr3·6H2O in a molar ratio of 3:1; the preparation atmosphere was replaced by an atmospheric environment.

[0050] Example 7

[0051] This example provides an organic-inorganic hybrid rare earth-based halide luminescent glass material BMI3EuCl6, which is prepared by referring to the method of Example 1. The difference from Example 1 is that the mixture of 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl) and EuCl3·6H2O in a molar ratio of 3:1 is replaced by the mixture of 1-butyl-3-methylimidazolium chloride (BMI HCl) and EuCl3·6H2O in a molar ratio of 3:1.

[0052] Example 8

[0053] This example provides a preparation method of an organic-inorganic hybrid rare earth-based halide luminescent glass material, including the following steps:

[0054] (1) Put 1-benzyl-2-methylimidazole (BnMelm) into a beaker, then add 5 mL of methanol and 1 mL of hydrochloric acid. After ultrasonic dissolution until complete, place it on a heating table at 80 °C until the solvent completely evaporates to obtain 1-benzyl-2-methylimidazolium chloride (BnMelm·HCl);

[0055] (2) Mix the 1-benzyl-2-methylimidazolium chloride (BnMelm·HCl) obtained in step (1) and EuCl3·6H2O in a molar ratio of 3:1, heat to 230 °C, keep warm for 20 min to obtain a uniform melt, and rapidly cool to room temperature in an air atmosphere after 180 s to obtain the organic-inorganic hybrid rare earth-based halide luminescent glass material, whose chemical general formula is BnMelm3EuCl6.

[0056] Example 9

[0057] This example provides an organic-inorganic hybrid rare earth-based halide luminescent glass material BnMelm3TbCl6, which is prepared by referring to the method of Example 8. The difference from Example 8 is that EuCl3·6H2O is replaced by TbCl3·6H2O.

[0058] Example 10

[0059] This example provides an organic-inorganic hybrid rare earth-based halide luminescent glass material Bzmim3CeBr6, which is prepared by referring to the method of Example 1. The difference from Example 1 is that the mixture of 1-benzyl-3-methylimidazolium chloride (Bzmim·HCl) and EuCl3·6H2O in a molar ratio of 3:1 is replaced by the mixture of 1-benzyl-3-methylimidazolium bromide (Bzmim HBr) and CeBr3·6H2O in a molar ratio of 3:1.

[0060] Comparative Example 1

[0061] A halide glass material with a chemical general formula of MTP3CeCl6, and its preparation method includes the following steps:

[0062] Mix methyltriphenylphosphonium chloride (MTP HCl) and CeCl3·6H2O in a molar ratio of 3:1, heat to 230 °C and keep warm for 20 min. After that, obvious particles exist in the melt. Subsequently, rapidly cool to room temperature within 180 s under an atmospheric atmosphere, and a transparent halide glass material cannot be obtained.

[0063] Comparative Example 2

[0064] A halide glass material with a chemical general formula of HTP3CeBr6, and its preparation method includes the following steps:

[0065] Mix hexyltriphenylphosphonium bromide (HTP HBr) and CeBr3·6H2O in a molar ratio of 3:1, heat to 260 °C and keep warm for 20 min. After that, a uniform melt is obtained. Subsequently, rapidly cool to room temperature within 180 s under an atmospheric atmosphere, and a completely transparent halide glass material cannot be obtained.

[0066] Comparative Example 3

[0067] A halide glass material with a chemical general formula of TBA3TbCl6, and its preparation method includes the following steps:

[0068] Mix tetrabutylammonium chloride (TBACl) and TbCl3·6H2O in a molar ratio of 3:1, heat to 140 °C and keep warm for 20 min. After that, a uniform melt is obtained. Subsequently, rapidly cool to room temperature within 180 s under an atmospheric atmosphere, and serious crystallization problems occur, and a glass material cannot be obtained.

[0069] Figure 1 Is the XRD pattern of the crystal materials prepared in Example 1 and Example 2. Figure 2 Are the thermogravimetric analysis and differential scanning calorimetry curves of the glass materials prepared in Example 1 and Example 2. Figure 3 Are the pictures of the glass materials prepared in Example 1 and Example 2 under 365 nm ultraviolet light. As can be seen from Figure 1 it, the Bzmim3EuCl6 and Bzmim3TbCl6 crystals obtained in Example 1 and Example 2 of the present invention have high purity. Figure 2 Shows that through differential scanning calorimetry technology, it is proved that the glass material has a relatively high glass transition temperature, excellent glass-forming ability, and can stably form a glassy structure. Figure 3 Shows that the Bzmim3EuCl6 and Bzmim3TbCl6 glasses obtained in Example 1 and Example 2 have the characteristics of high brightness, uniformity and transparency.

[0070] Figure 4Luminescence images of the glass materials obtained in Examples 3 - 5 under 365 nm ultraviolet light. a is Bzmim3Tb 0.75 Eu 0.25 Cl6 organic - inorganic hybrid rare - earth - based halide luminescent glass material and its picture under 365 nm excitation. b is Bzmim3Tb 0.5 Eu 0.5 Cl6 organic - inorganic hybrid rare - earth - based halide luminescent glass material and its picture under 365 nm excitation. c is Bzmim3Tb 0.25 Eu 0.75 Cl6 organic - inorganic hybrid rare - earth - based halide luminescent glass material and its picture under 365 nm excitation. It can be found that Figure 4 by adjusting the types and ratios of rare - earth metal ions in the material, different luminescent colors can be obtained. Figure 4 It shows that by adjusting the mixing ratio of Eu 3+ and Tb 3+ under 365 nm ultraviolet light excitation, a continuous change in luminescent color from green to red is achieved.

[0071] Figure 5 Luminescence image of the Hy3CeBr3 glass material in Example 6 under 365 nm ultraviolet light, Figure 5 showing that the glass material obtained in Example 6 emits weak light under 365 nm ultraviolet light.

[0072] Figure 6 Luminescence image of the BMI3EuCl6 glass material in Example 7 under 365 nm ultraviolet light, Figure 6 showing that the glass material obtained in Example 7 exhibits red luminescence and has high transparency under 365 nm ultraviolet light.

[0073] Figure 7 Luminescence images of the glass materials in Examples 8 and 9 under 365 nm ultraviolet light, Figure 7 showing that highly bright, uniform and transparent rare - earth halide glass materials are obtained in Examples 8 and 9 of the present invention.

[0074] Figure 8 Luminescence image of the Bzmim3CeBr6 glass material in Example 10 under 365 nm ultraviolet light, Figure 8 showing that after rapid cooling, a transparent and uniformly luminescent hybrid rare - earth halide glass can be obtained, which emits purple light at 365 nm, in line with the characteristic emission of Ce 3+ proving that the organic ligand reacts with the rare - earth metal ions.

[0075] Figure 9Emission diagram of the glass material of Comparative Example 1 under 365 nm ultraviolet light. As can be seen from Figure 9 it, using methyltriphenylphosphonium chloride as the organic ligand, a transparent halide glass cannot be obtained, and the emission under 365 nm is very weak.

[0076] Figure 10 Emission diagram of the glass material of Comparative Example 2 under 365 nm ultraviolet light. As can be seen from Figure 10 it, the emission of the glass material of Comparative Example 2 at 365 nm does not come from Ce 3+ , but from the organic component, which indicates that the organic ligand hexyltriphenylphosphonium bromide cannot react with rare earth metal ions.

[0077] Figure 11 Emission diagram of the glass material of Comparative Example 3 under 365 nm ultraviolet light. As can be seen from Figure 11 it, blue emission from the organic ligand rather than green emission from Tb 3+ is observed in the glass material of Comparative Example 3 at 365 nm, which indicates that the organic ligand cannot react with rare earth metal ions.

[0078] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An organic-inorganic hybrid rare earth-based halide luminescent glass material, characterized in that, Its chemical general formula is A x B y C z , where A is an organic cation containing an imidazole group or a pyridine group; B is a rare earth metal cation, C is a halogen anion, x = 3 - 4, y = 1, and z = 6 - 7.

2. The organic-inorganic hybrid rare earth-based halide luminescent glass material according to claim 1, wherein The A includes at least one of 1-benzyl-3-methylimidazole and its derivatives, 1-benzyl-2-methylimidazole and its derivatives, N-benzylimidazole and its derivatives, 1-butyl-3-methylimidazole and its derivatives, 1,3-dimethylimidazole and its derivatives, 1-ethyl-2,3-dimethylimidazole and its derivatives, benzimidazole and its derivatives, N-butylpyridinium bromide and its derivatives.

3. The organic-inorganic hybrid rare-earth-based halide luminescent glass material according to claim 1, characterized in that, The B includes at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium cations; and / or the C includes at least one of chlorine, bromine and iodine ions.

4. A method for preparing an organic-inorganic hybrid rare earth-based halide luminescent glass material according to any one of claims 1-3, characterized in that, Heat the crystal or powder of the chemical general formula A x B y C z to melting, and then cool it down to obtain the organic-inorganic hybrid rare earth-based halide luminescent glass material.

5. A method for preparing an organic-inorganic hybrid rare earth-based halide luminescent glass material according to any one of claims 1-3, characterized in that, It includes the following steps: According to the chemical general formula A x B y C z Weigh the halide salts of A and the halide salts of B respectively according to the stoichiometric ratio, mix them and heat to melting, then cool down to obtain the organic-inorganic hybrid rare earth-based halide luminescent glass material.

6. The preparation method of the organic-inorganic hybrid rare earth-based halide luminescent glass material according to claim 4 or 5, characterized in that, The temperature of the heating is 100°C - 280°C, and the time of the melting and heat preservation is 3 min - 60 min.

7. The method for preparing an organic-inorganic hybrid rare earth-based halide luminescent glass material according to claim 4 or 5, characterized in that, The time of the cooling is 3 s - 300 s.

8. The preparation method of the organic-inorganic hybrid rare earth-based halide luminescent glass material according to claim 4 or 5, characterized in that, The cooling is carried out in a protective atmosphere or an atmospheric atmosphere.

9. The preparation method of the organic-inorganic hybrid rare earth-based halide luminescent glass material according to claim 8, characterized in that, The protective atmosphere includes at least one of argon and nitrogen.

10. Use of the organic-inorganic hybrid rare earth-based halide luminescent glass material according to any one of claims 1 to 3, and the organic-inorganic hybrid rare earth-based halide luminescent glass material prepared by the preparation method of the organic-inorganic hybrid rare earth-based halide luminescent glass material according to any one of claims 4 to 9 in the fields of X-ray detection imaging, light-emitting diodes, optical temperature measurement, luminescent anti-counterfeiting, upconversion materials, and solid-state lighting.

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