Iron ion doped antimonate near-infrared afterglow luminescent material and preparation method thereof

Abstract

本发明提供了一种铁离子掺杂的锑酸盐近红外余辉发光材料及其制备方法，该发光材料的分子式可表示为：Sr2Lu1‑xSb1‑yO6:xFe3+,yA4+,yM+；A选自Ge、Zr、Sn或Si中的任意一种或多种；M选自Li、Na和K中的一种或多种；0＜x≤0.150，0＜y≤0.100。其中，Sr2Lu1‑xSb1‑yO6作为主体基质，给发光中心Fe3+提供合适的晶体场环境。A4+的掺杂使基质具有合适的陷阱，可以储存激发光的能量。M+的掺杂在材料中有着电荷平衡和助溶剂的作用。经测试，本发明提供的发光材料可发射宽带近红外光，其余辉至少可持续18h。

Description

Technical Field

[0001] This invention belongs to the field of rare earth luminescent materials technology, specifically relating to an iron ion-doped antimonate near-infrared afterglow luminescent material and its preparation method. Background Technology

[0002] In recent years, near-infrared light in the 650–1350 nm wavelength range, located within the "tissue transparency window," has been widely applied in many fields, such as health monitoring, night vision, and bioimaging, due to its high penetration into biological tissues. This high penetration allows for harmless and convenient imaging detection; therefore, the preparation and application of near-infrared materials are currently a hot research topic in the field of biofluorescence imaging both domestically and internationally.

[0003] Among near-infrared luminescent materials, near-infrared long-persistence materials are a special type of photoluminescent material. While being excited by external light, they can store a portion of the excitation energy and slowly release it as light radiation after the excitation stops. Therefore, near-infrared long-persistence materials can effectively avoid phototoxicity to biological tissues caused by in-situ excitation, reducing harm to organisms. Simultaneously, they overcome interference from stray light from the excitation light and the organism's own fluorescence on the detection signal, improving the signal-to-noise ratio of the detection results. This type of near-infrared long-persistence material, capable of enabling non-destructive, real-time, high-quality imaging of biological tissues, is key to solving the current problems restricting the development and application of fluorescence bioimaging technology.

[0004] However, most near-infrared long-afterglow luminescent materials currently used are Cr. 3+ Activated gallates or germanates are expensive, and although they have long near-infrared afterglow properties, these materials contain Cr. 3+ Oxidized to Cr 6+ Potential dangers. Cr 6+ Not only does it affect the luminescent properties of materials, but it can also easily penetrate human cells, damaging internal organs such as the liver, kidneys, and DNA, posing a certain degree of toxicity to organisms and the environment, leading to Cr... 3+ The applications of activated near-infrared long-afterglow luminescent materials are limited. Therefore, there is an urgent need to develop more environmentally friendly, healthier, lower-cost, and better-performing near-infrared long-afterglow luminescent materials. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide an iron-doped antimonate near-infrared afterglow luminescent material and its preparation method. The luminescent material exhibits good long afterglow properties and is inexpensive.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides an iron-doped antimonate near-infrared afterglow luminescent material, with the molecular formula: Sr₂Lu. 1-x Sb 1-y O6:xFe 3+ ,yA 4+ ,yM + ;

[0008] Wherein, A is selected from any one or more of Ge, Zr, Sn or Si; M is selected from one or more of Li, Na or K;

[0009] 0 < x ≤ 0.150, 0 < y ≤ 0.100.

[0010] Preferably, A is selected from Ge, Zr, Sn or Si; M is selected from Li, Na or K.

[0011] Preferably, 0.010 < x ≤ 0.100 and 0 < y ≤ 0.005.

[0012] Preferably, the iron-doped antimonate near-infrared afterglow luminescent material is selected from any one of the following molecular formulas:

[0013] Sr2Lu 0.999 Sb 0.999 O6:0.001Fe 3+ 0.001Ge 4+ 0.001Li + ;

[0014] Sr2Lu 0.993 Sb 0.999 O6:0.007Fe 3+ 0.001Ge 4+ 0.001Li + ;

[0015] Sr2Lu 0.900 Sb 0.999 O6:0.100Fe 3+ 0.001Ge 4+ 0.001Li + ;

[0016] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + ;

[0017] Sr2Lu 0.993 Sb 0.920 O6:0.007Fe 3+0.080Ge 4+ 0.080Li + ;

[0018] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Na + ;

[0019] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025K + ;

[0020] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Sn 4+ 0.025Li + ;

[0021] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Zr 4+ 0.025Li + ;

[0022] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Si 4+ 0.025Li + .

[0023] Secondly, the present invention provides a method for preparing the above-mentioned iron ion-doped antimonate near-infrared afterglow luminescent material, comprising the following steps:

[0024] A mixture is obtained by mixing a strontium source, a lutetium source, an antimony source, an iron source, a compound containing element A, and a compound containing element M.

[0025] The mixture was calcined to obtain an iron-doped antimonate near-infrared long afterglow luminescent material.

[0026] Preferably, the strontium source compound is selected from any one or more of strontium-containing oxides, strontium-containing carbonates, strontium-containing nitrates, strontium-containing oxalates, strontium-containing citrates, or strontium-containing acetates.

[0027] Preferably, the lutetium source compound is selected from one or more of lutetium-containing oxides, lutetium-containing hydroxides, lutetium-containing carbonates, lutetium-containing oxalates, lutetium-containing acetates, or lutetium-containing nitrates.

[0028] Preferably, the antimony source compound is selected from one or more of antimony-containing oxides, antimony-containing carbonates, antimony-containing oxalates, antimony-containing acetates, or antimony-containing nitrates.

[0029] Preferably, the iron source is selected from one or more of iron-containing oxides, iron-containing hydroxides, iron-containing halides, iron-containing oxalates, iron-containing acetates, or iron-containing nitrates.

[0030] Preferably, the compound containing element A is selected from one or more of oxides containing element A, hydroxides containing element A, halides containing element A, oxalates containing element A, acetates containing element A, or nitrates containing element A.

[0031] Preferably, the compound containing element M is selected from one or more of oxides containing element M, borates containing element M, hydroxides containing element M, halides containing element M, oxalates containing element M, acetates containing element M, or nitrates containing element M.

[0032] Preferably, the calcination temperature is 1000–1600℃ and the time is 0.5–24h.

[0033] Preferably, the calcination atmosphere is air, nitrogen, argon, or oxygen.

[0034] Preferably, the mixing process includes a first grinding process.

[0035] Preferably, the calcination process includes a second grinding process.

[0036] Preferably, the time for the first grinding treatment and the second grinding treatment is independently 5 to 120 minutes.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] This invention provides an iron-doped antimonate near-infrared afterglow luminescent material, the molecular formula of which can be represented as: Sr₂Lu 1-x Sb 1-y O6:xFe 3+ ,yA 4+ ,yM + Wherein, A is selected from any one or more of Ge, Zr, Sn, or Si; M is selected from one or more of Li, Na, and K; 0 < x ≤ 0.150, 0 < y ≤ 0.100. In this invention, Sr2Lu 1-x Sb1- y O6 serves as the main matrix, with Sr, Lu, and Sb forming part of the matrix, providing the luminescent centers with Fe. 3+ Providing a suitable crystal field environment allows Fe to 3+ It emits near-infrared light with a full width at half maximum (FWHM) of 110 nm at 890 nm. A 4+ The doping gives the matrix suitable traps to store the energy of the excitation light. Even after the light is removed, the luminescent material still emits light, displaying broadband near-infrared light. + The doping in the material plays a role in charge balance and as a cosolvent.

[0039] In summary, the iron-doped antimonate near-infrared long-afterglow luminescent material provided by this invention exhibits good long-afterglow phenomenon. According to tests, the luminescent material provided by this invention can emit broadband near-infrared light, and the afterglow can last for at least 18 hours.

[0040] In addition, the preparation method of the iron ion-doped antimonate near-infrared long afterglow luminescent material provided by the present invention is simple, with low raw material and equipment costs, non-toxic and non-polluting, non-radioactive, environmentally friendly, and highly reproducible. The resulting product has stable quality, is easy to operate and industrialize, and is suitable for widespread use. Attached Figure Description

[0041] Figure 1 Comparison of X-ray diffraction patterns of the near-infrared long-afterglow luminescent materials prepared in Examples 1-5 with those of the standard card;

[0042] Figure 2 The near-infrared long-afterglow luminescent material Sr2Lu prepared in Example 4 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + Excitation emission spectrum;

[0043] Figure 3 Comparison of emission spectra of near-infrared long afterglow materials prepared in Examples 1-3;

[0044] Figure 4 The near-infrared long-afterglow luminescent material Sr2Lu prepared in Example 4 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + Afterglow spectrum;

[0045] Figure 5The near-infrared long-afterglow luminescent material Sr2Lu prepared in Example 4 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + Macroscopic view of the afterglow of pink light in a photograph;

[0046] Figure 6 These are comparison images of the afterglow spectra of the near-infrared long afterglow materials prepared in Examples 2, 4, 5 and Comparative Example 1;

[0047] Figure 7 These are comparison images of the afterglow spectra of the near-infrared long afterglow materials prepared in Example 4 and Comparative Example 1;

[0048] Figure 8 These are comparative thermoluminescence curves of the near-infrared long afterglow powders prepared in Examples 2, 4, 5 and Comparative Example 1. Detailed Implementation

[0049] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0050] In existing technologies, near-infrared long-afterglow luminescent materials are mostly Cr. 3+ Activated gallates or germanates result in higher costs and the presence of Cr. 3+ Oxidized to Cr 6+ To address the problem, this invention provides an iron-doped antimonate near-infrared afterglow luminescent material, the molecular formula of which can be represented as: Sr₂Lu 1-x Sb 1-y O6:xFe 3+ ,yA 4+ ,yM + ;

[0051] Wherein, A is selected from any one or more of Ge, Zr, Sn or Si; M is selected from one or more of Li, Na or K;

[0052] 0 < x ≤ 0.150, 0 < y ≤ 0.100.

[0053] The iron-doped antimonate near-infrared afterglow luminescent material provided by this invention uses Sr2Lu 1-x Sb 1-y O6 serves as the main matrix, with Sr, Lu, and Sb forming part of the matrix, providing the luminescent centers with Fe.3+ Providing a suitable crystal field environment allows Fe to 3+ It emits near-infrared light with a full width at half maximum (FWHM) of 110 nm at 890 nm. A 4+ The doping gives the matrix suitable traps to store the energy of the excitation light. Even after the light is removed, the luminescent material still exhibits luminescence, emitting broadband near-infrared light. + The doping in the material plays a role in charge balance and as a cosolvent.

[0054] In some embodiments of the present invention, the iron-doped antimonate near-infrared afterglow luminescent material has the molecular formula shown above, wherein A is specifically selected from Ge, Zr, Sn, or Si; and M is specifically selected from Li, Na, or K. The values ​​0.010 < x ≤ 0.100 and 0 < y ≤ 0.005.

[0055] More specifically, in some specific embodiments of the present invention, the iron-doped antimonate near-infrared afterglow luminescent material is selected from any one of the following molecular formulas:

[0056] Sr2Lu 0.999 Sb 0.999 O6:0.001Fe 3+ 0.001Ge 4+ 0.001Li + ;

[0057] Sr2Lu 0.993 Sb 0.999 O6:0.007Fe 3+ 0.001Ge 4+ 0.001Li + ;

[0058] Sr2Lu 0.900 Sb 0.999 O6:0.100Fe 3+ 0.001Ge 4+ 0.001Li + ;

[0059] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + ;

[0060] Sr2Lu 0.993 Sb 0.920 O6:0.007Fe 3+ 0.080Ge 4+ 0.080Li +;

[0061] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Na + ;

[0062] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025K + ;

[0063] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Sn 4+ 0.025Li + ;

[0064] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Zr 4+ 0.025Li + ;

[0065] Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Si 4+ 0.025Li + .

[0066] The present invention also provides a method for preparing the above-mentioned iron ion-doped antimonate near-infrared afterglow luminescent material, comprising the following steps:

[0067] A mixture is obtained by mixing a strontium source, a lutetium source, an antimony source, an iron source, a compound containing element A, and a compound containing element M.

[0068] The mixture was calcined to obtain an iron-doped antimonate near-infrared long afterglow luminescent material.

[0069] In the above preparation method, the strontium source compound is preferably one or more of strontium-containing oxides, strontium-containing carbonates, strontium-containing nitrates, strontium-containing oxalates, strontium-containing citrates or strontium-containing acetates, and more preferably one or more of Sr(OH)2 or SrCO3.

[0070] The lutetium source compound is preferably one or more of lutetium-containing oxides, lutetium-containing hydroxides, lutetium-containing carbonates, lutetium-containing oxalates, lutetium-containing acetates, or lutetium-containing nitrates, and more preferably one or two of Lu2O3 or Lu2(CO3)3.

[0071] The antimony source compound is preferably one or more of antimony-containing oxides, antimony-containing carbonates, antimony-containing oxalates, antimony-containing acetates, or antimony-containing nitrates, and more preferably one or two of Sb₂O₃ or Sb₂O₅.

[0072] The iron source is preferably one or more of iron-containing oxides, iron-containing hydroxides, iron-containing halides, iron-containing oxalates, iron-containing acetates, or iron-containing nitrates, and more preferably one or two of Fe2O3 or Fe(OH)3.

[0073] The compound containing element A is preferably one or more of oxides, hydroxides, halides, oxalates, acetates, or nitrates containing element A, and more preferably one or more of GeO2, SnO2, ZrO2, or SiO2.

[0074] The compound containing element M is preferably one or more of oxides containing element M, borates containing element M, hydroxides containing element M, halides containing element M, oxalates containing element M, acetates containing element M, or nitrates containing element M, and more preferably one or more of Li2CO3, Li2B4O7, K2CO3, or Na2CO3.

[0075] After mixing the above raw materials, the resulting mixture is calcined according to the present invention to obtain the target product. In the present invention, the calcination temperature is 1000–1600°C, more preferably 1100–1500°C; including but not limited to 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, or 1600°C; the calcination time is preferably 0.5–24 hours; including but not limited to 0.5 hours, 6 hours, 12 hours, or 24 hours. Preferably, the calcination atmosphere is air, nitrogen, argon, or oxygen; more preferably air.

[0076] In some embodiments of the present invention, the mixing process preferably includes a first grinding process, the time of which is 5 to 120 minutes, including but not limited to 5 minutes, 10 minutes, 20 minutes, 30 minutes, 50 minutes, 80 minutes, 100 minutes, or 120 minutes.

[0077] In some embodiments of the present invention, the calcination process preferably includes a second grinding process, the time of which is 5 to 120 minutes, including but not limited to 5 minutes, 10 minutes, 20 minutes, 30 minutes, 50 minutes, 80 minutes, 100 minutes, or 120 minutes.

[0078] The point values ​​listed above in this invention are merely illustrative and not limited to these values; other point values ​​within the same range are also applicable. To avoid complexity, they will not be described in detail here.

[0079] Preferably, the apparatus for the first grinding process and the second grinding process in this invention is an agate mortar.

[0080] In some preferred embodiments of the present invention, the preparation method includes the following steps:

[0081] (1) Mix the strontium source compound, lutetium source compound, antimony source compound, iron-containing compound, A-containing compound and M-containing compound and grind for 5 to 120 minutes to obtain a raw material mixture;

[0082] (2) The raw material mixture obtained in step (1) is calcined in air at 1000-1600℃ for 0.5-24h, and then ground for 5-120min to obtain the near-infrared long afterglow luminescent material.

[0083] The preparation method provided by this invention is simple, with low cost of raw materials and equipment, non-toxic and non-polluting, non-radioactive, environmentally friendly, and highly reproducible. The resulting product has stable quality, is easy to operate and industrialize, and is suitable for widespread use.

[0084] To further illustrate the present invention, the following embodiments provide a detailed description. The experimental materials used in the following embodiments of the present invention are all commercially available products.

[0085] Example 1

[0086] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0087] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, GeO2 and Li2CO3 in a molar ratio of 2:0.999:0.999:0.001:0.001:0.001 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0088] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.999 Sb0.999 O6:0.001Fe 3+ 0.001Ge 4+ 0.001Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0089] Example 2

[0090] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0091] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, GeO2 and Li2CO3 in a molar ratio of 2:0.993:0.999:0.007:0.001:0.001 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0092] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.999 O6:0.007Fe 3+ 0.001Ge 4+ 0.001Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0093] Example 3

[0094] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0095] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, GeO2 and Li2CO3 in a molar ratio of 2:0.900:0.999:0.100:0.001:0.001 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0096] b) Grind the sintered body obtained in step a) into powder to obtain Sr2Lu with chemical composition. 0.900 Sb 0.999 O6:0.100Fe 3+ 0.001Ge 4+ 0.001Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0097] Example 4

[0098] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0099] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, GeO2 and Li2CO3 in a molar ratio of 2:0.993:0.975:0.007:0.025:0.025 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0100] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0101] Example 5

[0102] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0103] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, GeO2 and Li2CO3 in a molar ratio of 2:0.993:0.920:0.007:0.080:0.080 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0104] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.920 O6:0.007Fe 3+ 0.080Ge 4+ 0.080Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0105] Example 6

[0106] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0107] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, GeO2 and Na2CO3 in a molar ratio of 2:0.993:0.975:0.007:0.025:0.025 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0108] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Na + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0109] Example 7

[0110] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0111] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, GeO2 and K2CO3 in a molar ratio of 2:0.993:0.975:0.007:0.025:0.025 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0112] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025K + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0113] Example 8

[0114] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0115] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, SnO2 and Li2CO3 in a molar ratio of 2:0.993:0.975:0.007:0.025:0.025 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0116] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Sn 4+ 0.025Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0117] Example 9

[0118] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0119] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, ZrO2 and Li2CO3 in a molar ratio of 2:0.993:0.975:0.007:0.025:0.025 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0120] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Zr 4+ 0.025Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0121] Example 10

[0122] This embodiment provides an iron-doped antimonate near-infrared long-afterglow luminescent material, and the specific preparation method is as follows:

[0123] a) Take Sr2CO3, Lu2O3, Sb2O5, Fe2O3, SiO2 and Li2CO3 in a molar ratio of 2:0.993:0.975:0.007:0.025:0.025 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0124] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Si 4+ 0.025Li + Fe 3+ Doped antimonate near-infrared long afterglow luminescent materials.

[0125] Example 11

[0126] The only difference between this embodiment and Example 4 is that the strontium source compound in step a) is Sr(OH)2, while the other conditions and parameters are exactly the same as in Example 4.

[0127] Example 12

[0128] The only difference between this embodiment and Example 4 is that the lutetium source compound in step a) is Lu2(CO3)3, while the other conditions and parameters are exactly the same as in Example 4.

[0129] Example 13

[0130] The only difference between this embodiment and Embodiment 4 is that the antimony source compound in step a) is Sb2O3, while the other conditions and parameters are exactly the same as in Embodiment 4.

[0131] Example 14

[0132] The only difference between this embodiment and embodiment 4 is that the iron source compound in step a) is Fe(OH)3, while the other conditions and parameters are exactly the same as in embodiment 4.

[0133] Example 15

[0134] The only difference between this embodiment and Embodiment 4 is that the compound of the R source in step a) is Li2B4O7, while the other conditions and parameters are exactly the same as in Embodiment 4.

[0135] Example 16

[0136] The only difference between this embodiment and embodiment 4 is that the calcination temperature in step a) is 1000℃, while the other conditions and parameters are exactly the same as in embodiment 4.

[0137] Example 17

[0138] The only difference between this embodiment and embodiment 4 is that the calcination temperature in step a) is 1500℃, while the other conditions and parameters are exactly the same as in embodiment 4.

[0139] Example 18

[0140] The only difference between this embodiment and embodiment 4 is that the calcination temperature in step a) is 1600℃, while the other conditions and parameters are exactly the same as in embodiment 4.

[0141] Example 19

[0142] The only difference between this embodiment and embodiment 4 is that the grinding time in step a) is 120 minutes, while the other conditions and parameters are exactly the same as in embodiment 4.

[0143] Example 20

[0144] The only difference between this embodiment and embodiment 4 is that the grinding time in step a) is 60 minutes, while the other conditions and parameters are exactly the same as in embodiment 4.

[0145] Example 21

[0146] The only difference between this embodiment and embodiment 4 is that the grinding time in step a) is 5 minutes, while the other conditions and parameters are exactly the same as in embodiment 4.

[0147] Example 22

[0148] The only difference between this embodiment and embodiment 4 is that the calcination time in step a) is 0.5 h, while the other conditions and parameters are exactly the same as in embodiment 4.

[0149] Example 23

[0150] The only difference between this embodiment and embodiment 4 is that the calcination time in step a) is 12 hours, while the other conditions and parameters are exactly the same as in embodiment 4.

[0151] Example 24

[0152] The only difference between this embodiment and embodiment 4 is that the sintering atmosphere in step a) is oxygen, while the other conditions and parameters are exactly the same as in embodiment 4.

[0153] Example 25

[0154] The only difference between this embodiment and embodiment 4 is that the sintering atmosphere in step a) is nitrogen, while the other conditions and parameters are exactly the same as in embodiment 4.

[0155] Example 26

[0156] The only difference between this embodiment and embodiment 4 is that the sintering atmosphere in step a) is argon, while the other conditions and parameters are exactly the same as in embodiment 4.

[0157] Comparative Example 1

[0158] This comparative example provides an iron-doped antimonate material, and the specific preparation method is as follows:

[0159] a) Take Sr2CO3, Lu2O3, Sb2O5 and Fe2O3 in a molar ratio of 2:0.993:1:0.007 as raw materials, mix them evenly in an agate mortar and grind them for about 30 minutes, then put them into an alumina crucible and continue to calcine them at 1350℃ for 24 hours under air conditions, and then cool them to room temperature with the furnace.

[0160] b) Grind the sintered body obtained in step a) into powder to obtain the chemical composition Sr2Lu. 0.993 SbO6:0.007Fe 3 + Fe 3+ Doped antimonate materials.

[0161] Performance testing

[0162] The powders prepared in Examples 1-5 were subjected to X-ray diffraction, and the test results are as follows: Figure 1 As shown, the diffraction patterns of Examples 1-5 are consistent with the standard diffraction pattern (ICSD-257793), indicating that Fe... 3+ 、Ge 4+ and Li + Ion doping has almost no significant effect on the phase purity of the Sr₂LuSbO₆ host material. Therefore, it can be inferred that Fe 3+ 、Ge 4+ and Li + The ions are almost completely dissolved in the Sr2LuSbO6 main lattice.

[0163] The near-infrared long-afterglow luminescent material Sr2Lu prepared in Example 4 was used. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + The powder was subjected to fluorescence spectroscopy testing, and its excitation and emission spectra were as follows: Figure 2 As shown, by Figure 2 It can be seen that the excitation band of this material extends from 270nm to 400nm, and it can be effectively excited by near-ultraviolet light. The emission band peak is at about 890nm, and the half-maximum width is 110nm, indicating that the luminescent material emits broadband near-infrared light.

[0164] Fluorescence spectroscopy was performed on the near-infrared long-afterglow luminescent materials prepared in Examples 1-3. The test results are as follows: Figure 3 As shown, their spectral types are consistent, but their luminescence intensities differ. The only difference between Examples 1-3 is the Fe... 3+ Different concentrations can show Fe 3+ The concentration of [agent] has a significant impact on the luminescence intensity of the material.

[0165] The near-infrared long-afterglow luminescent material Sr2Lu prepared in Example 4 was used. 0.993 Sb 0.975 O6:0.007Fe 3+ 0.025Ge 4+ 0.025Li + The powder was irradiated with a 254nm UV lamp for 20 minutes, and the afterglow was measured. The afterglow spectrum is as follows: Figure 4 As shown, the afterglow spectrum exhibits a significant peak at 890 nm, indicating that this material possesses afterglow luminescence properties. Figure 5 It can be seen that the afterglow of the material can still be detected by the instrument after 18 hours, indicating that the afterglow of this material can last for at least 18 hours.

[0166] The powders prepared in Examples 2, 4, 5 and Comparative Example 1 were irradiated with a 254 nm ultraviolet lamp for 20 min, and afterglow was measured. The afterglow spectra are as follows: Figure 6 As shown, the afterglow intensity varies significantly. The difference between Examples 2, 4, 5 and Comparative Example 1 is that Comparative Example 1 does not contain Ge. 4+ and Li + The doping of Ge can be seen 4+ and Li + The presence of [something] has a significant impact on the intensity of the afterglow.

[0167] The powders prepared in Example 4 and Comparative Example 1 were irradiated with a 254 nm ultraviolet lamp for 20 min, and then afterglow was measured. The afterglow spectra are as follows: Figure 7 As shown, the afterglow intensity differs significantly between Example 4 and Comparative Example 1, specifically in Ge. 4+ and Li + Whether Ge is doped or not can be seen 4+ and Li + The doping has a significant impact on the afterglow intensity.

[0168] The afterglow is related to suitable traps, and thermoluminescence testing can reveal the depth and abundance of these traps. Powders prepared in Examples 2, 4, 5, and Comparative Example 1 were irradiated with a 254 nm UV lamp for 20 min, and then subjected to thermoluminescence testing. The thermoluminescence curves are shown below. Figure 8 As shown, their thermoluminescence intensities differ significantly. The difference between Examples 2, 4, 5 and Comparative Example 1 lies in Ge...4+ and Li + Whether Ge is doped or not can be seen 4+ and Li + The existence of this has a significant impact on the afterglow trap.

[0169] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An iron-doped antimonate near-infrared afterglow luminescent material, characterized in that, The molecular formula is represented as: Sr2Lu 1- x Sb 1-y O6:xFe 3+ ,yA 4+ ,yM + ; Wherein, A is selected from Ge; M is selected from Li; 0 < x ≤ 0.150, 0 < y ≤ 0.

100.

2. The iron-doped antimonate near-infrared afterglow luminescent material according to claim 1, characterized in that, 0.010 < x ≤ 0.100, 0 < y ≤ 0.

005.

3. The iron-doped antimonate near-infrared afterglow luminescent material according to claim 1, characterized in that, The iron-doped antimonate near-infrared afterglow luminescent material is selected from any one of the following molecular formulas: Sr2Lu 0.999 Sb 0.999 O6:0.001Fe 3+ ,0.001Ge 4+ ,0.001Li + ;Sr2Lu 0.993 Sb 0.999 O6:0.007Fe 3+ ,0.001Ge 4+ ,0.001Li + ; Sr2Lu 0.900 Sb 0.999 O6:0.100Fe 3+ ,0.001Ge 4+ ,0.001Li + ;Sr2Lu 0.993 Sb 0.975 O6:0.007Fe 3+ ,0.025Ge 4+ ,0.025Li + ;Sr2Lu 0.993 Sb 0.920 O6:0.007Fe 3+ ,0.080Ge 4 + ,0.080Li + 。 4. A method for preparing an iron-doped antimonate near-infrared afterglow luminescent material as described in any one of claims 1 to 3, characterized in that, Includes the following steps: A mixture is obtained by mixing a strontium source, a lutetium source, an antimony source, an iron source, a compound containing element A, and a compound containing element M. The mixture was calcined to obtain an iron-doped antimonate near-infrared long afterglow luminescent material.

5. The preparation method according to claim 4, characterized in that, The strontium source compound is selected from any one or more of strontium-containing oxides, strontium-containing carbonates, strontium-containing nitrates, strontium-containing oxalates, strontium-containing citrates, or strontium-containing acetates. The lutetium source compound is selected from one or more of lutetium-containing oxides, lutetium-containing hydroxides, lutetium-containing carbonates, lutetium-containing oxalates, lutetium-containing acetates, or lutetium-containing nitrates. The antimony source compound is selected from one or more of antimony-containing oxides, antimony-containing carbonates, antimony-containing oxalates, antimony-containing acetates, or antimony-containing nitrates. The iron source is selected from one or more of iron-containing oxides, iron-containing hydroxides, iron-containing halides, iron-containing oxalates, iron-containing acetates, or iron-containing nitrates. The compound containing element A is selected from one or more of the following: oxides containing element A, hydroxides containing element A, halides containing element A, oxalates containing element A, acetates containing element A, or nitrates containing element A. The compound containing element M is selected from one or more of the following: oxides containing element M, borates containing element M, hydroxides containing element M, halides containing element M, oxalates containing element M, acetates containing element M, or nitrates containing element M.

6. The preparation method according to claim 4 or 5, characterized in that, The calcination temperature is 1000~1600℃, and the time is 0.5~24 h.

7. The preparation method according to claim 4 or 5, characterized in that, The calcination atmosphere is air, nitrogen, argon, or oxygen.

8. The preparation method according to claim 4, characterized in that, The mixing process includes a first grinding process; The calcination process includes a second grinding process.

9. The preparation method according to claim 8, characterized in that, The time for the first grinding treatment and the second grinding treatment are each 5 to 120 minutes independently.

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