CN-121991126-A - Ionic rare earth complex scintillator glass and low-temperature melting preparation method and application thereof

CN121991126ACN 121991126 ACN121991126 ACN 121991126ACN-121991126-A

Abstract

The invention relates to the technical field of photoelectric materials and scintillators, and particularly discloses ion type rare earth complex scintillator glass, a low-temperature melting preparation method and application thereof. The invention develops a low-temperature melting quenching process, and directly melts and rapidly cools the crystalline ionic europium complex under the condition of no solvent, thereby realizing the direct preparation of the transparent scintillator glass of the ionic rare earth complex. The prepared glass scintillator material has high transparency, high luminous efficiency, high rare earth content and excellent processability, fundamentally eliminates light scattering caused by particle aggregation and phase separation in the traditional composite film, and breaks through the concentration quenching limit. The glass scintillator material shows excellent luminescence performance under the excitation of X rays, and can remarkably improve imaging resolution and detection sensitivity. The invention provides a feasible technical path for the development of novel rare earth scintillator materials, and has important application prospects in the fields of medical imaging, nondestructive testing, high-energy radiation detection and the like.

Inventors

WU YIMING
WANG SHENGHUA
QUAN XIN
WANG YIWEN
XIE LUQI
PANG HONG
YU HAO
XU JIAHUI

Assignees

厦门大学

Dates

Publication Date: 20260508
Application Date: 20260407

Claims (7)

1. The low-temperature melting preparation method of the ionic rare earth complex scintillator glass is characterized by comprising the following steps of: s1, respectively dissolving a beta-diketone ligand, alkali, europium metal salt and a quaternary phosphonium salt according to the molar ratio of 4:4:1:1, adding an alkali solution into the beta-diketone ligand solution to make the beta-diketone ligand be salinized, sequentially adding the quaternary phosphonium salt solution and the europium metal salt solution, reacting to generate a precipitate, separating and vacuum drying to obtain ionic europium complex powder; s2, recrystallizing and purifying the ionic europium complex powder to obtain crystalline ionic europium complex; s3, heating the crystalline ionic europium complex to 180-220 ℃ to enable the crystalline ionic europium complex to be melted into liquid, and then placing the liquid in a room temperature environment for rapid quenching and demoulding to obtain the ionic rare earth complex scintillator glass; The beta-diketone ligand is selected from one of 4, 4-trifluoro-1- (2-naphthyl) -1, 3-butanedione, 4-trifluoro-1-phenyl-1, 3-butanedione or 2-thiophenyl formyl trifluoroacetone, and the quaternary phosphine salt is selected from one of tetraphenyl phosphine chloride, propyl triphenyl phosphine bromide, butyl triphenyl phosphine chloride or benzyl triphenyl phosphine chloride.
2. The method according to claim 1, wherein the alkali in step S1 is sodium hydroxide and the europium metal salt is europium chloride.
3. The method according to claim 1, wherein the recrystallization purification in step S2 is performed by dissolving the europium ion complex powder in methylene chloride, adding petroleum ether, standing for crystallization, separating and drying, wherein the addition amount of petroleum ether is 3 times the volume of methylene chloride.
4. The method according to claim 1, wherein the alkali solution is prepared by dissolving the alkali in water, the europium metal salt solution is prepared by dissolving the europium metal salt in water, the β -diketone ligand solution is prepared by dissolving the β -diketone ligand in ethanol, and the quaternary phosphonium salt solution is prepared by dissolving the quaternary phosphonium salt in ethanol.
5. An ionic rare earth complex scintillator glass prepared by the low temperature melting preparation method of any one of claims 1 to 4.
6. The ionic rare earth complex scintillator glass of claim 5, comprising the structural formula: ; wherein A is europium metal, L is beta-diketone ligand, B + is quaternary phosphine salt cation, the beta-diketone ligand is one of 4, 4-trifluoro-1- (2-naphthyl) -1, 3-butanedione, 4-trifluoro-1-phenyl-1, 3-butanedione or 2-thiophenyl formyl trifluoroacetone, and the quaternary phosphine salt is one of tetraphenyl phosphine chloride cation, propyl triphenyl phosphine bromide cation, butyl triphenyl phosphine chloride cation or benzyl triphenyl phosphine chloride cation.
7. Use of an ionic rare earth complex scintillator glass prepared by a low temperature melt preparation method as claimed in any one of claims 1-4 in the preparation of a radiation detection device.

Description

Ionic rare earth complex scintillator glass and low-temperature melting preparation method and application thereof Technical Field The invention relates to the technical field of photoelectric materials and scintillators, in particular to an ionic rare earth complex scintillator transparent glass, a low-temperature melting preparation method and application thereof. Background The X-ray imaging technique has an indispensable role in the fields of medical diagnosis, industrial nondestructive inspection, safety inspection, high-energy physical experiments, and the like. The core is that after X-ray penetrates the object to be measured, the scintillator absorbs high-energy photons and converts the photons into visible light signals, and then the visible light signals are converted into electric signals through the photoelectric detector to form an image. The performance of the scintillator directly affects the resolution, sensitivity, and reliability of the imaging system. In recent years, metal-organic hybrid materials have been a hot spot for scintillator research due to their tunable structure and excellent luminescence properties. The rare earth metal-organic complex has the advantages of simple synthesis, large Stokes displacement, narrow emission peak, high structural stability, heavy atom content and the like, and has great potential as a new generation scintillator material. However, the practical use of existing rare earth complex scintillators still faces significant challenges. The current research focuses on covalent rare earth complexes, which are usually incorporated into polymer matrices to prepare scintillator films, but the compatibility of such complexes with polymer matrices is limited, and efficient and uniform compounding is difficult to achieve. For example, two rare earth complexes of Tb xEu1-x BPTC (non-patent document 1) and Tb xEu1-x BDC (non-patent document 2) reported in the prior art are physically blended with Polydimethylsiloxane (PDMS) to prepare a scintillation film. However, due to poor compatibility of the rare earth complex crystal and PDMS, complex crystallization, void formation and agglomeration are inevitably caused under high doping amount, serious light scattering is caused, the transparency of the film is reduced, and finally the imaging resolution is damaged. To improve the dispersibility, researchers have tried to dissolve the complex and then complex it with the polymer. For example, academic papers (non-patent document 3) and various patents (e.g., patent document 1, patent document 2, and patent document 3) disclose methods for preparing thin films and scintillator fibers by dissolving a covalent rare earth complex (e.g., rare earth europium β -diketone complex) in an organic solvent and then incorporating the complex into a polymer such as PMMA or PS. However, such methods are limited by the solubility and compatibility of the complex in the polymer, and only low concentrations of doping (typically less than 10%) can be achieved. Under high doping concentration, the complex is easy to agglomerate and phase separate, light scattering centers are reintroduced, concentration quenching is possibly caused (namely, the distance between light emitting centers is too short, non-radiation transmission of energy among the centers is quickened, and the light emitting intensity is reduced), so that high light emitting efficiency and high optical transparency cannot be achieved. Further, there have been attempts to prepare an intrinsic transparent film by modifying an organic ligand by linking a long chain or a bulky group thereto and by a method of rapid cooling after heating and melting (non-patent document 4). However, the ligand modification strategy can change the electron cloud distribution of the ligand, destroy the sensitization capability of the organic ligand to rare earth ions, lead to the photoluminescence quantum yield of the material to be only 30% -32%, and the luminescence behavior of the scintillator under the excitation of X rays is not yet studied. The ionic rare earth organic complex has better solubility in theory, and provides possibility for preparing high-concentration doped films. However, the introduction of flexible organic cation counter ions in the system can intensify molecular vibration, and the non-radiative transition is enhanced, so that the photoluminescence quantum yield of the material is generally low, and is usually only about 50% (non-patent document 5, non-patent document 6 and non-patent document 7). The latest report (patent document 4) is that long-chain organic cations with the carbon number of C 8~C20 are adopted to prepare an ionic rare earth organic complex transparent scintillator film with the doping content of 30% -60%, but how to create a rare earth organic scintillator film with high luminous quantum yield and intrinsic transparent characteristics has not been reported yet. To fundamentally solve the problem of dispersibil