CN113667469A - 一种提高闪烁体x射线探测性能的制备方法 - Google Patents
一种提高闪烁体x射线探测性能的制备方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 6
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- 229940044658 gallium nitrate Drugs 0.000 claims description 3
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- HBROZNQEVUILML-UHFFFAOYSA-N salicylhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1O HBROZNQEVUILML-UHFFFAOYSA-N 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052771 Terbium Inorganic materials 0.000 abstract description 26
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 abstract description 24
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Abstract
本发明公开了一种提高闪烁体X射线探测性能的制备方法，用三正辛基氧化膦对一种铽配合物样品产生表面钝化作用，使其X射线致发光强度提高了约81.8％，与商用CSI(Tl)闪烁体的X射线致发光强度相当，并且对X射线有良好的线性响应，检测极限达到0.146μGy s‑1，比常用的X射线治疗剂量率低38倍。本发明为高性能闪烁体材料的设计提供新的思路，有望在低剂量X射线探测领域得到广泛应用。
Description
技术领域
本发明属于闪烁体的设计与应用研究领域，尤其涉及一种提高X射线探测性能的闪烁体材料的制备方法与应用研究。
背景技术
基于闪烁体的X射线探测广泛应用于生物成像、无损检测、天文探测等领域。近年来，卤化物钙钛矿、陶瓷等闪烁体材料发展迅速。然而，现有的闪烁体材料仍然存在许多问题和局限性。例如钙钛矿闪烁体中含有铅等有毒重金属离子掺杂，陶瓷闪烁体需要在高温下制备。因此，寻找低成本、高性能的闪烁材料具有重要的科学和实践意义。
稀土元素具有尖锐的发射峰、较长的发光寿命和强光漂白性，在各个领域有广泛的应用。根据拉波特定则，以稀土元素为发光中心的闪烁体材料的光产额较低，在实际应用中并不理想。因此，需要通过有效的手段增强现有闪烁体材料的X射线探测能力，以实现对低剂量X射线更灵敏、更准确的探测。
发明内容
本发明的一个目的是提供一种提高闪烁体材料X射线探测性能的技术，以稀土铽离子为发射中心，通过三正辛基氧化膦的表面钝化作用增强了铽离子在X射线激发下的特征发射，以实现对低剂量率X射线的灵敏检测。这种闪烁体材料光产额约为9000photonsMev-1，表现出对X射线具有良好的线性响应，检测限约为0.146μGy s-1，比常用的X射线诊疗剂量低38倍。
本发明的另外一个目的是提供所述的闪烁体材料的制备方法，该方法包括以下的步骤：
1)将硝酸铽、硝酸镓、水杨羟肟酸、苯甲酸钠按照1:4:12的份数比例充分混合，再加入3880份甲醇搅拌过夜得到透明溶液A。
2)在步骤1)获得的溶液A中加入97份吡啶，继续搅拌15分钟得到半透明乳浊液。
3)将权利要求2)中的溶液过滤，得到透明溶液B并在室温下静置若干天，直到其中析出淡黄色晶体。
4)取步骤3)获得的透明溶液B和三正辛基氧化膦按照250:1的液固比(mL:g)混合，并搅拌10分钟。
5)将步骤2)所得的晶体加入步骤4)所得的溶液中，静置2～4小时后滤去溶液，得到最终产物。
本发明的方法的优点是成本低、环保、无需高温条件。
本发明的提供所述的闪烁体材料用于X射线检测中的应用。
附图说明
图1：实施例1中铽配合物的X射线衍射图。
图2：实施例1中铽配合物的元素分布及能谱图。
图3：实施例1中铽配合物的扫描电镜图。
图4：实施例1中铽配合物和实例2中表面钝化的铽配合物的X射线激发光谱图，其中商用闪烁体CSI(Tl)作为对照。
图5：实施例2中表面钝化的铽配合物的X射线致发光强度与X射线剂量率的线性关系图。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。
实施例1：本实施例铽配合物，化学式TbGa4(shi)4(C6H5CO2)4(C5H5N)(CH3OH)。
铽配合物的制备：
将硝酸铽、硝酸镓、水杨羟肟酸、苯甲酸钠按照1:4:12的份数比例充分混合，再加入3880份甲醇搅拌过夜得到透明溶液A。在溶液A中加入97份吡啶，继续搅拌15分钟得到半透明乳浊液。将乳浊液滤去沉淀后得到透明溶液B。将溶液B静置数天得到最终产物铽配合物。
图1为本实施例样品的X-射线粉末衍射图，从图中可以看出所制备的样品的X-射线粉末衍射峰和文献(Chow CY,et al.Ga3+/Ln3+Metallacrowns:a promising family ofhighly luminescent lanthanide complexes that covers visible and nearinfrareddomains.J.Am.Chem.Soc.138,5100-5109(2016).)中的标准样品相吻合，表明材料制备成功。
图2为本实施例样品的扫描电镜图，从图中可以看出该晶体为层状结构。
图3为本实施例得到的晶体的元素分布及能谱图，从图中可以看出该晶体的元素组成主要有铽(Tb)、镓(Ga)等。
实施例2：本实施例表面钝化的铽配合物闪烁体。
表面钝化的铽配合物闪烁体的制备：将实施例1中的溶液B和三正辛基氧化膦按照250:1的液固比(mL:g)混合后搅拌10分钟，得到溶液C。将实施例1的产物铽配合物晶体加入至溶液C中，静置2～4小时，滤去溶液后得到最终产物表面钝化的铽配合物闪烁体。
图4为本实施例和实施例1样品的X射线激发光谱图，商用闪烁体CSI(Tl)被用于对比。从图中可以看出本实施例的表面钝化的铽配合物样品比实施例1的铽配合物样品有更强的发射峰，其中表面钝化的铽配合物样品在545纳米发射峰处的发光强度比未经表面钝化的铽配合物样品高了81.8％，与CSI(Tl)在520纳米发射峰处的强度相当。
图5为本实施例中表面钝化的铽配合物样品的X射线致发光强度与X射线剂量率的线性关系图。从图中可以看出，在0.24～20.6μGy s-1的X射线激发下，表面钝化的铽配合物闪烁体对X射线有良好的线性响应，计算得到检测限为0.146μGy s-1，比常用的X射线诊疗剂量低38倍。
上面对本发明的具体实施例作了详细说明，但是本发明并不限于上述实施例，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (3)
1.一种提高闪烁体X射线探测性能的制备方法。其特征在于：用三正辛基氧化膦对晶体样品产生表面钝化作用，得到的闪烁体材料的X射线致发光强度实现大幅度提高。
2.根据权利要求1所述的闪烁体材料制备方法，其特征在于，包括以下步骤：
1)将硝酸铽、硝酸镓、水杨羟肟酸、苯甲酸钠按照1:4:12的份数比例充分混合，再加入3880份甲醇搅拌过夜得到透明溶液A。
2)在步骤1)获得的溶液A中加入97份吡啶，继续搅拌15分钟得到半透明乳浊液。
3)将权利要求2)中的溶液过滤，得到透明溶液B并在室温下静置若干天，直到其中析出淡黄色晶体。
4)取步骤3)获得的透明溶液B和三正辛基氧化膦按照250:1的液固比(mL:g)混合，并搅拌10分钟。
5)将步骤2)所得的晶体加入步骤4)所得的溶液中，静置2～4小时后滤去溶液，得到最终产物。
3.权利要求1所述的闪烁体材料用于X射线探测中的应用。
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| CN114773618A (zh) * | 2022-05-12 | 2022-07-22 | 中国计量大学 | 一种稀土-有机荧光和闪烁材料的制备方法及应用 |
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| US20170137710A1 (en) * | 2014-04-08 | 2017-05-18 | Ns Materials Inc. | Quantum dot, manufacturing method of the dot, and compact, sheet member, wavelength conversion member and light emitting apparatus using the quantum dot |
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| US20170137710A1 (en) * | 2014-04-08 | 2017-05-18 | Ns Materials Inc. | Quantum dot, manufacturing method of the dot, and compact, sheet member, wavelength conversion member and light emitting apparatus using the quantum dot |
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| CN114773618B (zh) * | 2022-05-12 | 2023-11-03 | 中国计量大学 | 一种稀土-有机荧光和闪烁材料的制备方法及应用 |
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