Yb < 3 + >-doped oxyfluoride scintillation glass capable of avoiding visible light crosstalk, optical fiber and preparation method and application of Yb < 3 + >-doped oxyfluoride scintillation glass

Abstract

The invention belongs to the field of radiation detection and X-ray imaging, and discloses Yb < 3 + > doped oxyfluoride scintillation glass capable of avoiding visible light crosstalk, an optical fiber and a preparation method and application of the Yb < 3 + > doped oxyfluoride scintillation glass. The scintillation glass is prepared from the following raw materials in percentage by mole: 5 to 30 percent of high atomic number element compound, 0.01 to 10 percent of alkali metal compound, 45 to 70 percent of silicon dioxide, 5 to 25 percent of aluminum compound and 0.01 to 2 percent of externally doped Yb < 3 + > source, wherein the sum of the components is 100 percent. The Yb < 3 + > doped oxyfluoride glass and the optical fiber thereof have excellent optical performance and environmental stability, and X-ray imaging capable of avoiding visible light crosstalk can be realized by combining the Yb < 3 + > doped oxyfluoride glass with a 900nm long-pass filter. In addition, the Yb < 3 + >-doped infrared band scintillation optical fiber has lower transmission loss compared with a visible band emission scintillation optical fiber, and can be used in the related fields of environmental monitoring, X-ray imaging, industrial detection and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of radiation monitoring and X-ray imaging, and in particular to a Yb 3+ Fluorine-doped oxyfluoride scintillating glass, optical fiber and preparation method and application thereof. BACKGROUND

[0002] Scintillator materials play an irreplaceable role in key fields such as radiological imaging, high-energy physics experiments, nuclear safety monitoring and security inspection. Its core function is to efficiently convert high-energy ionizing radiation into visible light signals, thereby realizing the detection and imaging of radiation energy. At present, the research of scintillators mainly focuses on scintillator materials that emit in the visible band (380-780 nm). Many crystals, glasses, ceramics and plastics that emit in this band and have excellent scintillation performance have been developed. However, the luminescence characteristics of scintillators in the visible light band can easily cause significant photon scattering and optical crosstalk between pixels, resulting in a decrease in spatial resolution and an increase in noise of the imaging system, especially in high-density pixelated detectors (such as CMOS / CCD arrays and SPAD arrays). At present, it is also difficult to achieve clear X-ray imaging under visible light interference. Near-infrared (NIR, 780-1700 nm) scintillators have become a new breakthrough direction for future scintillator development due to their ability to avoid visible light crosstalk, deep penetration ability, and high spectral matching with silicon-based photodetectors (such as InGaAs). For example, Wang et al. developed a Tm-doped near-infrared emitting halide scintillator, which can reduce visible light crosstalk in X-ray imaging to some extent, but the imaging effect under visible light is still poor [DOI: 10.1002 / adfm.202401995]. In addition, some scholars (such as Yanagida et al. in Japan, DOI: 10.1016 / j.radphyschem.2025.11287) have proposed that, compared with visible band emitting scintillating fibers, infrared scintillating fibers have stronger long-distance low-loss transmission capability, providing better material selection for distributed radiation monitoring and remote imaging systems, and having important significance in nuclear industry safety monitoring and deep space exploration. However, there is no good near-infrared scintillating glass fiber reported.

[0003] In summary, there is currently no scintillator that can achieve good imaging effect under visible light interference, and there is also a lack of a glass fiber that can achieve long-distance low transmission loss. It is of great significance to develop a glass fiber that can achieve clear X-ray imaging under visible light interference and has low transmission loss. SUMMARY

[0004] In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present application is to provide a Yb 3+Fluoride oxydoped scintillating glass.

[0005] Another object of the present application is to provide a Yb 3+ Method for preparing fluoride oxydoped scintillating glass.

[0006] Another object of the present application is to provide a Yb 3+ Fluoride oxydoped scintillating glass optical fiber.

[0007] Still another object of the present application is to provide a Yb 3+ Method for preparing fluoride oxydoped scintillating glass optical fiber.

[0008] Yet another object of the present application is to provide the above Yb 3+ Fluoride oxydoped scintillating glass and Yb 3+ Application of fluoride oxydoped scintillating glass optical fiber.

[0009] Yb 3+ The fluoride oxydoped glass and its optical fiber have excellent high-temperature resistance, radiation resistance and X-ray detection performance, and by adding a 900nm long-pass filter in front of a CMOS camera, the problem of visible light crosstalk in X-ray imaging can be effectively solved. 3+ Transmission loss of doped scintillating optical fiber. The present application provides a new material selection for radiation detection under high temperature, high dose and long distance transmission conditions and X-ray imaging to avoid visible light crosstalk.

[0010] The object of the present application is achieved by the following technical solutions:

[0011] A Yb 3+ The fluoride oxydoped scintillating glass has a raw material molar percentage composition of:

[0012] Compound of high atomic number element: 5-30%;

[0013] Alkali metal compound: 0.01-10%:

[0014] Silicon dioxide: 45-70%;

[0015] Aluminum compound: 5-25%, the sum of the above components is 100%;

[0016] External doping Yb 3+ Source: 0.01-2mol%.

[0017] Preferably, the Yb 3+ The molar percentage composition of the fluoride oxydoped scintillating glass is:

[0018] Compound of high atomic number element: 10-30%;

[0019] Alkali metal compound: 5-10%;

[0020] Silicon dioxide: 55-70%;

[0021] Aluminum compound: 5-15%, the sum of the above components being 100%;

[0022] External doping Yb 3+ Source: 0.02-1.2 mol%;

[0023] The high atomic number element is a metal element with atomic number ≥ 50.

[0024] Preferably, the compound of the high atomic number element is at least one of the fluorides or oxides of Cs, Ba, La, Gd, Lu elements;

[0025] The alkali metal compound is at least one of the oxides, fluorides or carbonates of alkali metals; the alkali metal is at least one of Li, Na, K;

[0026] The aluminum compound is an oxide or fluoride of aluminum;

[0027] The Yb 3+ Source is introduced through Yb2O3 or YbF3.

[0028] Preferably, the Yb 3+ The mole percentage of fluoride in the Yb

[0029] The Yb 3+ The Yb

[0030] A method for preparing a Yb 3+ fluoride oxide scintillating glass, comprising the following steps:

[0031] The raw materials are weighed in terms of mole percentage, ground and mixed uniformly, melted to obtain a glass liquid, cooled and shaped to obtain a transparent block-shaped glass, and then annealed to obtain a Yb 3+ fluoride oxide scintillating glass;

[0032] The melting conditions are: 1400-1650℃ melting for 10-60min;

[0033] The annealing conditions are: 400-600℃ annealing for 6-20h.

[0034] A Yb 3+A fluorine-doped oxyfluoride scintillating glass optical fiber comprises a core and a cladding.

[0035] The core is Yb 3+ The cladding is quartz glass.

[0036] Preferably, the diameter of the optical fiber is 125-800 mu m.

[0037] A Yb 3+ A preparation method of a fluorine-doped oxyfluoride scintillating glass optical fiber comprises the following steps:

[0038] (1) Preparation of core glass: the bulk glass prepared by the above method or Yb 3+ The fluorine-doped oxyfluoride scintillating glass is used as the core glass.

[0039] (2) Preform assembly: the core glass prepared in step (1) is processed into a glass rod or ground into powder and filled into a tubular cladding material to obtain an optical fiber preform.

[0040] (3) Optical fiber drawing: the optical fiber preform prepared in step (2) is softened and drawn to obtain the optical fiber.

[0041] Preferably, the melting temperature in step (1) is 1400-1650 DEG C.

[0042] The softening condition in step (3) is 1900-2050 DEG C for 10-30 min, and the drawing speed is 5-30 m / min.

[0043] The Yb 3+ The fluorine-doped oxyfluoride glass or the Yb 3+ The fluorine-doped oxyfluoride glass optical fiber is applied to the fields of environmental monitoring, radiation detection, X-ray imaging under visible light interference.

[0044] The Yb 3+ The fluorine-doped oxyfluoride scintillating glass and the optical fiber have excellent high-temperature resistance and radiation resistance. By adding a 900 nm long-pass filter in front of a CMOS camera, the problem of visible light crosstalk in X-ray imaging can be effectively solved. The near-infrared scintillating glass optical fiber has a transmission loss lower than that of Ce 3+ The Yb 3+ The fluorine-doped oxyfluoride glass and the optical fiber have application scenarios in radiation detection under high temperature, high dose and long-distance transmission and X-ray imaging avoiding visible light crosstalk.

[0045] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0046] (1) The Yb 3+ The fluorine oxide doped scintillation glass and optical fiber have the characteristics of strong component adjustability and simple preparation process, can realize preparation of large-size samples, and are low in production cost and convenient for scale industrial production.

[0047] (2) The Yb 3+ The fluorine oxide doped scintillation glass and optical fiber can effectively solve the common visible light crosstalk problem in X-ray imaging by being combined with a 900 nm long-pass filter.

[0048] (3) The Yb 3+ The fluorine oxide doped scintillation glass optical fiber has a transmission loss in a near-infrared wave band that is much lower than a transmission loss in a visible wave band, and is suitable for long-distance radiation detection.

[0049] (4) The Yb 3+ The fluorine oxide doped scintillation glass and optical fiber have excellent high-temperature resistance and radiation resistance, and can be used under harsh conditions such as high temperature and high dose. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 The Yb 3+ Optical transmission spectrum of the fluorine oxide doped scintillation glass;

[0051] Figure 2 The Yb 3+ Photoluminescence spectrum of the fluorine oxide doped scintillation glass;

[0052] Figure 3 The Yb 3+ X-ray excitation emission spectrum of the fluorine oxide doped scintillation glass;

[0053] Figure 4 The Yb 3+ X-ray imaging effect diagram of the fluorine oxide doped scintillation glass under darkroom conditions and white light LED irradiation conditions;

[0054] Figure 5 The Yb 3+ Radiation resistance test results of the fluorine oxide doped scintillation glass;

[0055] Figure 6 The Yb 3+ High-temperature resistance test results of the fluorine oxide doped scintillation glass;

[0056] Figure 7 The Yb 3+ Optical microscope photo of the fluorine oxide doped scintillation glass optical fiber;

[0057] Figure 8 Yb prepared for Example 1 3+ Photoluminescence spectra of fluorine oxide doped scintillating glass optical fiber;

[0058] Figure 9 Yb prepared for Example 1 3+ X-ray excitation emission spectra of fluorine oxide doped scintillating glass optical fiber;

[0059] Figure 10 Yb prepared for Example 1 3+ Loss test results of fluorine oxide doped scintillating glass optical fiber;

[0060] Figure 11 Yb prepared for Example 2 3+ X-ray excitation emission spectra of fluorine oxide doped scintillating glass;

[0061] Figure 12 Yb prepared for Example 2 3+ X-ray imaging effect of fluorine oxide doped scintillating glass under darkroom condition and white light LED irradiation condition;

[0062] Figure 13 Yb prepared for Example 2 3+ X-ray excitation emission spectra of fluorine oxide doped scintillating glass optical fiber;

[0063] Figure 14 Yb prepared for Example 1 3 Loss test results of fluorine oxide doped scintillating glass optical fiber;

[0064] Figure 15 Yb prepared for Example 3 3 X-ray excitation emission spectra of fluorine oxide doped scintillating glass;

[0065] Figure 16 Yb prepared for Example 3 3+ X-ray imaging effect of fluorine oxide doped scintillating glass under darkroom condition and white light LED irradiation condition;

[0066] Figure 17 Yb prepared for Example 3 3+ X-ray excitation emission spectra of fluorine oxide doped scintillating glass optical fiber;

[0067] Figure 18 Yb prepared for Example 4 3+ X-ray excitation emission spectra of fluorine oxide doped scintillating glass;

[0068] Figure 19 Yb prepared for Example 43+ X-ray imaging effect diagram of fluorine-doped oxyfluoride scintillating glass under darkroom condition and white light LED irradiation condition;

[0069] Figure 20 Yb prepared for Example 4 3+ X-ray excitation emission spectrum of fluorine-doped oxyfluoride scintillating glass optical fiber;

[0070] Figure 21 Yb prepared for Comparative Example 1 3+ X-ray excitation emission spectrum of fluorine-doped oxyfluoride scintillating glass;

[0071] Figure 22 Yb prepared for Comparative Example 1 3+ X-ray imaging effect diagram of fluorine-doped oxyfluoride scintillating glass under darkroom condition and white light LED irradiation condition;

[0072] Figure 23 Yb prepared for Comparative Example 1 3+ Loss test results of fluorine-doped oxyfluoride scintillating glass optical fiber;

[0073] Figure 24 Yb prepared for Comparative Example 1 3+ X-ray excitation emission spectrum of fluorine-doped oxyfluoride scintillating glass;

[0074] Figure 25 Yb prepared for Comparative Example 2 3+ X-ray imaging effect diagram of fluorine-doped oxyfluoride scintillating glass under darkroom condition and white light LED irradiation condition;

[0075] Figure 26 Linear absorption coefficient of Comparative Example 3 sample and comparison with common scintillating crystals;

[0076] Figure 27 Glass sample photo of Comparative Example 4;

[0077] Figure 28 Sample photo of Comparative Example 5;

[0078] Figure 29 Annealing photo of Comparative Example 6 at 200℃;

[0079] Figure 30 Annealing photo of Comparative Example 6 at 800℃. DETAILED DESCRIPTION

[0080] The application will be further described in conjunction with the examples and the accompanying drawings of the specification, but the embodiments of the application are not limited thereto. For the process parameters not specifically mentioned, the conventional techniques can be referred to.

[0081] Example 1

[0082] The embodiment provides a Yb 3+ The preparation method of the fluorine oxide doped scintillation glass and optical fiber comprises the following steps:

[0083] The powder medicines of LaF3, KF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0084] LaF3: 30%

[0085] KF: 5%

[0086] SiO2: 55%

[0087] Al2O3: 10%

[0088] YF3: 0.1%

[0089] (1) After being fully ground for 30 min, the raw materials are placed in a corundum crucible and melted at 1500 DEG C for 30 min, so that a glass liquid is obtained;

[0090] (2) The glass liquid obtained in (1) is poured onto a stainless steel plate to be cooled and formed, so that a transparent glass block is obtained;

[0091] (3) The transparent glass block obtained in (2) is annealed at 450 DEG C for 10 h, so that a Yb 3+ The fluorine oxide doped scintillation glass.

[0092] The preparation method of the optical fiber comprises the following steps:

[0093] (1) The powder medicines of LaF3, KF, SiO2, Al2O3 and YF3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0094] LaF3: 30%

[0095] KF: 5%

[0096] SiO2: 55%

[0097] AlF3: 10%

[0098] YF3: 0.1%

[0099] The raw materials with a total weight of 20 g are weighed, the raw materials are fully mixed and ground in an agate mortar for 30 min, the raw materials are placed in a corundum crucible and melted at 1500 DEG C in an atmospheric atmosphere for 30 min, and the glass liquid in a molten state is poured on a preheated copper plate, so that a core glass is obtained.

[0100] (2) The core glass in step (1) or the Yb3+ The fluorine-doped oxyfluoride scintillating glass is processed into a cylindrical shape and placed in a quartz glass tube. The core glass has a diameter of 2.3 mm and a length of 40 mm. The quartz tube has an outer diameter of 20 mm and an inner diameter of 2.5 mm. One side of the hollow quartz tube is sealed to complete the preparation of the preform.

[0101] (3) The preform in step (2) is placed in the furnace of the drawing tower and rapidly heated to 1900°C at a rate of 200°C / min for 10 min. The drawing speed is 5-30 m / min. The diameter of the optical fiber after drawing is 125 μm-500 μm.

[0102] The Yb 3+ The fluorine-doped oxyfluoride scintillating glass and the optical fiber are characterized, Figure 1 The Yb 3 + The optical transmission spectrum of the fluorine-doped oxyfluoride scintillating glass can be seen to have a transmission rate of up to 90%, proving that the bulk glass has excellent optical transmission performance. High optical transmission is conducive to radiation detection performance and X-ray imaging effects. Figure 2 The Yb 3 The photoluminescence spectrum of the fluorine-doped oxyfluoride scintillating glass can be seen to have near-infrared fluorescence emission in the range of 900 nm-1100 nm. Figure 3 The Yb 3+ The X-ray excitation emission spectrum of the fluorine-doped oxyfluoride scintillating glass can be seen to have near-infrared fluorescence emission in the range of 900 nm-1100 nm, similar to photoluminescence. Figure 4 The Yb 3+ The X-ray imaging effect of the fluorine-doped oxyfluoride scintillating glass under darkroom conditions and white light LED irradiation conditions can be seen. By adding a 900 nm long-pass filter in front of the camera, clear X-ray imaging can be achieved even under visible light source interference. Figure 5 The Yb 3+ The radiation resistance test results of the fluorine-doped oxyfluoride scintillating glass can be seen. Even after 4000 s of irradiation, the luminescence intensity of the glass can still be maintained at the initial value. Figure 6 The Yb 3+ The high temperature resistance test results of the fluorine-doped oxyfluoride scintillating glass can be seen. Even at a high temperature of 350°C, the luminescence intensity of the glass can still be maintained at about 77% of the initial value.

[0103] Figure 7 The Yb 3+ Optical microscope photo of the fluorine-doped oxyfluoride scintillating glass optical fiber. Figure 8 The Yb 3+The photoluminescence spectrum of the fluorine oxide doped scintillating glass fiber can be seen in the near infrared fluorescence emission in the range of 900nm-1100nm. Figure 9 Yb prepared for Example 1 3+ The X-ray excitation emission spectrum of the fluorine oxide doped scintillating glass fiber can be seen in the near infrared fluorescence emission in the range of 900nm-1100nm similar to the photoluminescence. Figure 10 Yb prepared for Example 1 3+ The loss test result of the fluorine oxide doped scintillating glass fiber is 17.91dB / m at 1064nm, which is more than 1 times lower than the same system Ce 3+ The transmission loss of the doped fiber (43.87dB / m@470nm) is more than 1 times lower.

[0104] Example 1 proves that Yb 3+ The fluorine oxide doped scintillating glass and fiber have excellent scintillation performance, which can realize radiation detection under the conditions of high temperature, high dose, long distance transmission and X-ray imaging under visible light crosstalk.

[0105] Example 2

[0106] The present embodiment provides a Yb 3+ The preparation method of the fluorine oxide doped scintillating glass and fiber, first the preparation method of the glass includes the following steps:

[0107] The powder medicines of BaO, CsF, KF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0108] BaO: 2.5%

[0109] CsF: 2.5%

[0110] KF: 10%

[0111] SiO2: 70%

[0112] Al2O3: 15%

[0113] Yb2O3: 0.6%

[0114] (1) After 30min of grinding, it is placed in a corundum crucible and melted at 1600℃ for 30min, and a glass liquid is obtained;

[0115] (2) Pour the glass liquid obtained in (1) onto a stainless steel plate to cool and form a transparent glass block;

[0116] (3) The transparent glass block obtained in (2) is annealed at 500℃ for 10h to obtain Yb 3+Fluoride-doped oxyfluoride scintillating glass.

[0117] The method for preparing the optical fiber comprises the following steps:

[0118] (1) Selecting BaO, CsF, KF, SiO2, Al2O3 and Yb2O3 powder medicines with a purity of 99.99%, and the raw materials are in the following molar ratio:

[0119] BaO: 2.5%

[0120] CsF: 2.5%

[0121] KF: 10%

[0122] SiO2: 60%

[0123] Al2O3: 15%

[0124] Yb2O3: 0.6%

[0125] The total weight of the raw materials is 20 g, the raw materials are mixed and ground in a agate mortar for 30 min, the raw materials are placed in a corundum crucible and melted at 1600 DEG C in an atmospheric atmosphere for 30 min, and the molten glass liquid is poured on a preheated copper plate to obtain a core glass.

[0126] (2) The core glass in step (1) or the Yb 3+ The fluoride-doped oxyfluoride scintillating glass is processed into a cylindrical shape and placed in a quartz glass tube, the core glass has a diameter of 2.3 mm and a length of 40 mm, the quartz tube has an outer diameter of 20 mm and an inner diameter of 2.5 mm, one side of the hollow quartz tube is sealed, and the preparation of the preform rod is completed.

[0127] (3) The preform rod in step (2) is placed in the furnace of the drawing tower, rapidly heated to 1950 DEG C at a rate of 200 DEG C / min and kept for 10 min, the drawing speed is 5-30 m / min, and the diameter of the optical fiber after drawing is 125-500 μm.

[0128] The prepared Yb 3+ The fluoride-doped oxyfluoride scintillating glass and the optical fiber are characterized, Figure 11 The X-ray excitation emission spectrum of the Yb 3+ The fluoride-doped oxyfluoride scintillating glass of Example 2 can be seen in the near-infrared fluorescence emission in the range of 900 nm-1100 nm. Figure 12 The X-ray imaging effect diagram of the Yb 3+ The fluoride-doped oxyfluoride scintillating glass of Example 2 under darkroom conditions and white light LED irradiation conditions can be seen, by adding a 900 nm long-pass filter in front of the camera, clear X-ray imaging can be realized even under visible light source interference. Figure 13Yb prepared in Example 2 3+ The X-ray excitation emission spectrum of the fluorine oxide doped scintillating glass fiber can be seen that the near-infrared fluorescent emission in the range of 900nm-1100nm similar to photoluminescence. Figure 14 Yb prepared in Example 2 3+ The loss test result of the fluorine oxide doped scintillating glass fiber is 16.80dB / m at 1064nm.

[0129] Example 2 proves that Yb 3+ The fluorine oxide doped scintillating glass and fiber have excellent scintillation performance, and can realize X-ray imaging under visible light crosstalk and fiber transmission.

[0130] Example 3

[0131] The embodiment provides a Yb 3+ The preparation method of the fluorine oxide doped scintillating glass and fiber, first, the preparation method of the glass comprises the following steps:

[0132] The powder medicines of Gd2O3, NaF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0133] Gd2O3: 17%

[0134] NaF: 8%

[0135] SiO2: 60%

[0136] Al2O3: 15%

[0137] Yb2O3: 1%

[0138] (1) After being fully ground for 30min, the mixture is placed in a corundum crucible and melted at 1600℃ for 30min, to obtain a glass liquid;

[0139] (2) The glass liquid obtained in (1) is poured onto a stainless steel plate to be cooled and formed, to obtain a transparent glass block;

[0140] (3) The transparent glass block obtained in (2) is annealed at 500℃ for 10h, to obtain Yb 3+ fluorine oxide doped scintillating glass.

[0141] The preparation method of the fiber comprises the following steps:

[0142] (1) The powder medicines of Gd2O3, NaF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0143] Gd2O3: 17%

[0144] NaF: 8%

[0145] SiO2: 60%

[0146] Al2O3: 15%

[0147] Yb2O3: 1%

[0148] The raw materials with a total weight of 20 g were weighed, and the raw materials were mixed and ground in a corundum mortar for 30 min. The raw materials were placed in a corundum crucible and melted at 1600°C in an atmospheric atmosphere for 30 min. The molten glass liquid was poured onto a preheated copper plate to obtain a core glass.

[0149] (2) The core glass in step (1) or the Yb 3+ The fluorine oxide doped scintillation glass was processed into a cylindrical shape and placed in a quartz glass tube. The core glass had a diameter of 2.3 mm and a length of 40 mm. The quartz tube had an outer diameter of 20 mm and an inner diameter of 2.5 mm. One side of the hollow quartz tube was sealed to complete the preparation of the preform rod.

[0150] (3) The preform rod in step (2) was placed in the furnace of the drawing tower and rapidly heated to 1950°C at a rate of 200°C / min and kept for 10 min. The drawing speed was 5-30 m / min. After drawing, the diameter of the optical fiber was 125-500 μm.

[0151] The prepared Yb 3+ The fluorine oxide doped scintillation glass and the optical fiber were characterized, Figure 15 The X-ray excitation emission spectrum of the Yb 3+ The fluorine oxide doped scintillation glass prepared in Example 3 showed near-infrared fluorescence emission in the range of 900 nm-1100 nm. Figure 16 The X-ray imaging effect of the Yb 3+ The fluorine oxide doped scintillation glass prepared in Example 3 showed near-infrared fluorescence emission in the range of 900 nm-1100 nm. Figure 17 The X-ray excitation emission spectrum of the Yb 3+ The fluorine oxide doped scintillation glass optical fiber showed near-infrared fluorescence emission in the range of 900 nm-1100 nm similar to photoluminescence.

[0152] Example 3 proved that the Yb 3+ The fluorine oxide doped scintillation glass and the optical fiber had excellent scintillation performance and could realize X-ray imaging under visible light interference and optical fiber transmission.

[0153] Example 4

[0154] The embodiment provides a Yb 3+ The preparation method of the fluorine oxide doped scintillation glass and the optical fiber comprises the following steps:

[0155] The powder medicines of Lu2O3, Li2CO3, SiO2, AlF3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0156] Lu2O3: 20%

[0157] Li2CO3: 10%

[0158] SiO2: 55%

[0159] AlF3: 15%

[0160] Yb2O3: 0.01%

[0161] (1) After being fully ground for 30 min, the raw materials are placed in a corundum crucible and melted at 1600 DEG C for 30 min, so that a glass liquid is obtained;

[0162] (2) The glass liquid obtained in (1) is poured onto a stainless steel plate to be cooled and formed, so that a transparent glass block is obtained;

[0163] (3) The transparent glass block obtained in (2) is annealed at 500 DEG C for 10 h, so that a Yb 3+ The fluorine oxide doped scintillation glass.

[0164] The preparation method of the optical fiber comprises the following steps:

[0165] (1) The powder medicines of Lu2O3, Li2CO3, SiO2, AlF3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0166] Lu2O3: 20%

[0167] Li2CO3: 10%

[0168] SiO2: 55%

[0169] AlF3: 15%

[0170] Yb2O3: 0.01%

[0171] The raw materials with a total weight of 20 g are weighed, the raw materials are fully mixed and ground in an agate mortar for 30 min, the raw materials are placed in a corundum crucible and melted at 1600 DEG C in an atmospheric atmosphere for 30 min, and the glass liquid in a molten state is poured on a preheated copper plate, so that a core glass is obtained.

[0172] (2) The core glass in step (1) or the Yb 3+ The fluorine oxide doped scintillation glass is processed into a cylindrical shape and placed in a quartz glass tube. The core glass has a diameter of 2.3 mm and a length of 40 mm. The quartz tube has an outer diameter of 20 mm and an inner diameter of 2.5 mm. One side of the hollow quartz tube is sealed to complete the preparation of the preform rod.

[0173] (3) The preform rod in step (2) is placed in the furnace of the drawing tower and rapidly heated to 1950°C at a rate of 200°C / min for 10 min. The drawing speed is 5-30 m / min. The diameter of the optical fiber after drawing is 125-500 μm.

[0174] The prepared Yb 3+ The fluorine oxide doped scintillation glass and the optical fiber are characterized, Figure 18 The Yb 3+ The X-ray excitation emission spectrum of the fluorine oxide doped scintillation glass shows near-infrared fluorescence emission in the range of 900-1100 nm. Figure 19 The Yb 3+ The X-ray imaging effect diagram of the fluorine oxide doped scintillation glass under dark room conditions and white light LED irradiation conditions shows that clear X-ray imaging can be achieved even under visible light source interference by adding a 900 nm long pass filter in front of the camera. Figure 20 The Yb 3+ The X-ray excitation emission spectrum of the fluorine oxide doped scintillation glass fiber shows near-infrared fluorescence emission in the range of 900-1100 nm similar to photoluminescence.

[0175] Example 4 proves that the Yb 3+ The fluorine oxide doped scintillation glass and the optical fiber have excellent scintillation performance and can realize radiation detection under high temperature, high dose, long distance transmission and X-ray imaging under visible light interference.

[0176] Comparative Example 1

[0177] When Yb 3+ Ce 3+ The preparation method of the fluorine oxide doped scintillation glass and the optical fiber comprises the following steps:

[0178] Pure LaF3, KF, SiO2, Al2O3 and Ce2O3 powder medicines with a purity of 99.99% are selected. The raw materials are calculated according to the following molar ratio:

[0179] LaF3: 15%

[0180] KF: 5%

[0181] SiO2: 65%

[0182] Al2O3: 15%

[0183] Ce2O3: 0.1%

[0184] (1) After being fully ground for 30 min, the glass was placed in a corundum crucible and was placed under carbon powder reduction conditions at 1500°C for 30 min for melting to obtain a glass liquid;

[0185] (2) The glass liquid obtained in (1) was poured onto a stainless steel plate to cool and form a transparent glass block;

[0186] (3) The transparent glass block obtained in (2) was annealed at 450°C for 10 h to obtain Ce 3+ fluorine oxide doped scintillation glass;

[0187] The method for preparing the optical fiber comprises the following steps:

[0188] (1) The powder medicines of LaF3, KF, SiO2, Al2O3 and Ce2O3 with a purity of 99.99% were selected, and the raw materials were calculated according to the following molar ratio:

[0189] LaF3: 15%

[0190] KF: 5%

[0191] SiO2: 65%

[0192] Al2O3: 15%

[0193] Ce2O3: 0.1%

[0194] The raw materials with a total weight of 20 g were weighed, were fully mixed and ground in an agate mortar for 30 min, were placed in a corundum crucible and were melted at 1500°C under C powder reduction for 30 min, and the molten glass liquid was poured on a preheated copper plate to obtain a core glass.

[0195] (2) The core glass in step (1) was processed into a cylindrical shape and was placed in a quartz glass tube, the core glass had a diameter of 2.3 mm and a length of 40 mm, the quartz tube had an outer diameter of 20 mm and an inner diameter of 2.5 mm, and one side of the hollow quartz tube was sealed to complete the preparation of the preform rod.

[0196] (3) The preform rod in step (2) was placed in a drawing tower furnace, was rapidly heated to 1900°C at a rate of 200°C / min and was kept for 10 min, the drawing speed was 5-30 m / min, and the diameter of the optical fiber after drawing was 125 μm-500 μm.

[0197] The prepared Ce 3+ The fluorine-doped oxyfluoride scintillating glass and optical fiber are characterized, Figure 21 The prepared Ce 3+ The X-ray excitation emission spectrum of the fluorine-doped oxyfluoride scintillating glass shows that the glass has a visible band emission in the range of 300 nm-600 nm. Figure 22 The prepared Ce 3+ The X-ray imaging effect diagram of the fluorine-doped oxyfluoride scintillating glass under darkroom conditions and white light LED irradiation conditions shows that X-ray imaging cannot be achieved under light interference. Figure 23 The prepared Ce 3+ The loss test results of the fluorine-doped oxyfluoride scintillating glass optical fiber show that the transmission loss 43.87 dB / m@470 nm is much higher than that of Yb 3+ doped fluorine-doped oxyfluoride scintillating glass optical fiber.

[0198] The fluorine-doped oxyfluoride scintillating glass with visible band short emission doped with the luminescent ion Ce 3+ of Example 1 cannot achieve Yb 3+ doped fluorine-doped oxyfluoride scintillating glass can achieve X-ray imaging under visible light crosstalk, and the optical fiber transmission loss under conditions such as long-distance transmission is also much higher than that of Yb 3+ doped fluorine-doped oxyfluoride scintillating glass optical fiber.

[0199] Example 2

[0200] When the Yb 3+ doping concentration is too high, a Yb 3+ doped fluorine-doped oxyfluoride scintillating glass preparation method, the glass preparation method comprises the following steps:

[0201] The powder medicines of LaF3, KF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0202] LaF3: 15%

[0203] KF: 5%

[0204] SiO2: 65%

[0205] Al2O3: 15%

[0206] Yb2O3: 10%

[0207] (1) After 30 min of grinding, place in a corundum crucible, melt at 1500℃ for 30 min, and get the glass liquid;

[0208] (2) pour the glass liquid obtained in (1) onto a stainless steel plate to cool and form a transparent glass block;

[0209] (3) anneal the transparent glass block obtained in (2) at 450℃ for 10h to obtain Ce 3+ fluoride oxy-oxide doped scintillation glass;

[0210] The prepared Yb 3+ fluoride oxy-oxide doped scintillation glass is characterized, Figure 24 The Yb 3+ fluoride oxy-oxide doped scintillation glass prepared in Comparative Example 2 has a weak emission in the range of 900nm-1200nm. Figure 25 The Yb 3+ fluoride oxy-oxide doped scintillation glass prepared in Comparative Example 2 has a weak emission in the range of 900nm-1200nm.

[0211] Because the glass has a weak emission, the corresponding optical fiber does not need to be prepared.

[0212] Comparative Example 2 proves that when the Yb 3+ doping concentration is too high, the sample has a weak emission, and the X-ray imaging effect under dark conditions and visible light conditions is poor.

[0213] Comparative Example 3

[0214] When a large amount of low-atomic-number compounds are used, a Yb 3+ fluoride oxy-oxide doped scintillation glass is provided, and a preparation method of the glass comprises the following steps:

[0215] MgO, LiF, SiO2, Al2O3 and Yb2O3 powder medicines with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0216] MgO: 15%

[0217] LiF: 5%

[0218] SiO2: 65%

[0219] Al2O3: 15%

[0220] Yb2O3: 0.3%

[0221] (1) After being fully ground for 30min, the mixture is placed in a corundum crucible, melted at 1650℃ for 30min, and a glass liquid is obtained;

[0222] (2) The glass liquid obtained in (1) is poured onto a stainless steel plate to cool and form a transparent glass block;

[0223] (3) The transparent glass block obtained in (2) is annealed at 450℃ for 10h to obtain Yb 3+ fluoride oxide doped scintillation glass;

[0224] Figure 26 The linear absorption coefficient of this sample is compared with that of common scintillation crystals Bi4Ge3O 12 (BGO) and Gd3Al2Ga3O 12 (GAGG). As shown in the figure, the linear absorption of the compound with a large amount of low atomic number is much lower than that of the common scintillation crystal, and the X-ray absorption capacity is poor.

[0225] Comparative Example 4

[0226] When the glass former SiO2 content is low or the high atomic number compound content is too high, a Yb 3+ fluoride oxide doped scintillation glass is provided. The preparation method of the glass comprises the following steps:

[0227] The powder medicines of BaO, KF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0228] BaO: 40%

[0229] KF: 10%

[0230] SiO2: 35%

[0231] Al2O3: 15%

[0232] Yb2O3: 0.5%

[0233] (1) After being fully ground for 30min, the mixture is placed in a corundum crucible and melted at 1650℃ for 30min to obtain a glass liquid;

[0234] (2) The glass liquid obtained in (1) is poured onto a stainless steel plate to cool and form a transparent glass block.

[0235] Figure 27 The photo of the glass sample of Comparative Example 4 shows that the raw materials cannot form a glass due to the low content of the glass former SiO2 and the high content of the high atomic number compound element.

[0236] Comparative Example 5

[0237] When the melting temperature is too low, the powder medicines of LaF3, KF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are in the following molar ratio:

[0238] LaF3: 15%

[0239] KF: 5%

[0240] SiO2: 65%

[0241] Al2O3: 15%

[0242] Yb2O3: 10%

[0243] After being fully ground for 30 min, the sample is placed in a corundum crucible and melted at 1100°C for 30 min. The glass cannot be melted, and the raw materials are only sintered into blocks, Figure 28 The sample of Comparative Example 5.

[0244] Comparative Example 6

[0245] When the annealing temperature is too high (for example, 800°C) or too low (for example, 100°C), the powder medicines of LaF3, KF, SiO2, Al2O3 and Yb2O3 with a purity of 99.99% are selected, and the raw materials are in the following molar ratio:

[0246] LaF3: 15%

[0247] KF: 5%

[0248] SiO2: 65%

[0249] Al2O3: 15%

[0250] Yb2O3: 1%

[0251] (1) After being fully ground for 30 min, the sample is placed in a corundum crucible and melted at 1500°C for 30 min to obtain a glass liquid;

[0252] (2) The glass liquid obtained in (1) is poured onto a stainless steel plate to cool and form a transparent glass block;

[0253] (3) The transparent glass block obtained in (2) is annealed at 200°C / 800°C for 10 h to obtain Yb 3+ fluoride oxyhalide doped scintillation glass;

[0254] When annealed at 200°C, the internal stress cannot be eliminated, the glass is easy to burst when polished, and a large block cannot be formed. Figure 29 The sample of Comparative Example 6 annealed at 200°C.

[0255] When annealed at 800℃, the glass is seriously crystallized in the interior, which leads to the decrease of transparency and affects the imaging effect. Figure 30 The photograph of Comparative Example 6 annealed at 800℃.

[0256] The above examples are cases of implementation of the present application, but the implementation of the present application is not limited by the examples. Any changes, modifications, substitutions, combinations, simplifications, etc. made without departing from the spirit and principles of the present application should be equivalent replacement methods and are included in the protection scope of the present application.

Claims

1. A Yb 3+ Oxyfluoride-doped scintillating glass, characterized in that The raw material molar percentage composition is: Compounds of elements with high atomic numbers: 5-30%; Alkali metal compounds: 0.01-10% Silicon dioxide: 45-70%; Aluminum compound: 5-25%, the sum of the above components is 100%; Yb-doped 3+ Source: 0.01~2mol%.

2. Yb according to claim 1 3+ Oxyfluoride-doped scintillating glass, characterized in that The Yb 3+ The molar percentage composition of the fluoride-doped oxyscintillating glass is: Compounds of elements with high atomic numbers: 10-30%; Alkali metal compounds: 5-10%; Silicon dioxide: 55-70%; Aluminum compound: 5-15%, the sum of the above components is 100%; Yb-doped 3+ Source: 0.02~1.2mol%; The high atomic number element is a metal element with an atomic number ≥50.

3. Yb according to claim 1 3+ Oxyfluoride-doped scintillating glass, characterized in that The compound of the high atomic number element is at least one of the fluorides or oxides corresponding to Cs, Ba, La, Gd, and Lu; The alkali metal compound is at least one of an oxide, a fluoride or a carbonate corresponding to the alkali metal; The alkali metal is at least one of Li, Na, and K; The aluminum compound is aluminum oxide or fluoride; The Yb 3+ The source is introduced through Yb2O3 or YbF3.

4. Yb according to any one of claims 1 to 3 3+ Oxyfluoride-doped scintillating glass, characterized in that The Yb 3+ The mole percentage of fluoride in the fluoride-doped oxyfluoride scintillating glass is 8 to 35%, and the mole percentage of oxide is 65 to 92%; The Yb 3+ When excited by X-rays or xenon lamps, the emission peak of fluoride-doped oxyfluoride scintillating glass is located at 900nm-1100nm.

5. Yb according to any one of claims 1 to 4 3+ The method for preparing fluoride-doped oxyfluoride scintillating glass is characterized in that: The following steps are involved: The raw materials are weighed by molar percentage, ground and mixed evenly, melted to obtain glass liquid, cooled and formed into transparent block glass, and then annealed to obtain Yb 3+ doped oxyfluoride scintillating glass; The melting conditions are: melting at 1400-1650°C for 10-60 minutes; The annealing conditions are: annealing at 400-600° C. for 6-20 hours.

6. A Yb 3+ Oxyfluoride-doped scintillating glass optical fiber, characterized in that Includes core and cladding; The core is the Yb as claimed in any one of claims 1 to 4 3+ doped oxyfluoride scintillating glass; The cladding is made of quartz glass.

7. Yb according to claim 6 3+ Oxyfluoride-doped scintillating glass optical fiber, characterized in that The diameter of the optical fiber is 125-800 μm.

8. Yb according to any one of claims 6 to 7 3+ The preparation method of fluoride-doped oxyscintillating glass optical fiber is characterized in that: The steps include: (1) Preparation of core glass: The bulk glass or Yb 3+ Oxyfluoride-doped scintillating glass is used as the core glass; (2) Preform assembly: processing the core glass of step (1) into a glass rod or grinding it into powder and then filling it into a tubular cladding material to obtain an optical fiber preform; (3) Fiber drawing: The fiber preform rod described in step (2) is softened and drawn to obtain the optical fiber.

9. Yb according to claim 8 3+ The preparation method of fluoride-doped oxyscintillating glass optical fiber is characterized in that: The melting temperature in step (1) is 1400-1650° C. The softening condition in step (3) is 1900-2050° C. for 10-30 min, and the drawing speed is 5-30 m / min.

10. Yb according to any one of claims 1 to 4 3+ Doped oxyfluoride glass or Yb as claimed in any one of claims 6 to 7 3+ Applications of fluoride-doped glass fibers in environmental monitoring, radiation detection, and X-ray imaging under visible light interference.

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