CN113667469B - 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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- 238000001514 detection method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 13
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002161 passivation Methods 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- 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
- 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
- 238000002156 mixing Methods 0.000 claims 3
- 229910052771 Terbium Inorganic materials 0.000 abstract description 23
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 abstract description 21
- 239000012467 final product Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000003745 diagnosis Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- -1 rare earth terbium ions Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004875 x-ray luminescence Methods 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 150000001217 Terbium Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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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 (1)
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,得到的闪烁体材料实现了X射线致发光强度提高,对X射线剂量的检测限达到0.148μGy s-1,适用于X射线探测领域,制备方法包括以下步骤:
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2748份甲醇搅拌过夜得到透明溶液A;
2)将步骤1)获得的溶液A和吡啶按照28:1的份数比例混合,继续搅拌15分钟得到半透明乳浊液;
3)将步骤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1597:1的份数比例充分混合,并搅拌10分钟;
5)将步骤3)所得的晶体加入步骤4)所得的溶液中进行表面钝化,静置2-4小时后滤去溶液,得到最终晶体产物。
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