CN116103045B - 一种LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料及其制备方法和应用 - Google Patents
一种LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料及其制备方法和应用 Download PDFInfo
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- 230000003287 optical effect Effects 0.000 title claims abstract description 78
- 239000011232 storage material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000003860 storage Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 14
- 229910001940 europium oxide Inorganic materials 0.000 claims description 14
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 229910052693 Europium Inorganic materials 0.000 claims description 12
- 229910003443 lutetium oxide Inorganic materials 0.000 claims description 10
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 claims description 10
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 238000003384 imaging method Methods 0.000 claims description 5
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 5
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- APFWLFUGBMRXCS-UHFFFAOYSA-N 4,7-dihydroxy-3-phenylchromen-2-one Chemical compound O=C1OC2=CC(O)=CC=C2C(O)=C1C1=CC=CC=C1 APFWLFUGBMRXCS-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 229950010610 lutetium chloride Drugs 0.000 claims description 2
- AEDROEGYZIARPU-UHFFFAOYSA-K lutetium(iii) chloride Chemical compound Cl[Lu](Cl)Cl AEDROEGYZIARPU-UHFFFAOYSA-K 0.000 claims description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- BOTHRHRVFIZTGG-UHFFFAOYSA-K praseodymium(3+);trifluoride Chemical compound F[Pr](F)F BOTHRHRVFIZTGG-UHFFFAOYSA-K 0.000 claims description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 claims description 2
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 2
- CUDGTZJYMWAJFV-UHFFFAOYSA-N tetraiodogermane Chemical compound I[Ge](I)(I)I CUDGTZJYMWAJFV-UHFFFAOYSA-N 0.000 claims description 2
- HPNURIVGONRLQI-UHFFFAOYSA-K trifluoroeuropium Chemical compound F[Eu](F)F HPNURIVGONRLQI-UHFFFAOYSA-K 0.000 claims description 2
- LKNRQYTYDPPUOX-UHFFFAOYSA-K trifluoroterbium Chemical compound F[Tb](F)F LKNRQYTYDPPUOX-UHFFFAOYSA-K 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 2
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Abstract
本发明属于长余辉发光材料的技术领域，公开了一种经掺杂的LiSc1‑xLuxGeO4光存储材料及其制备方法，其化学通式为LiSc1‑xLuxGeO4:yLn3+,zEu3+(Ln＝Tb,Pr,or Bi)；其制备方法是根据元素摩尔比Li:Sc:Lu:Ge:O:Ln:Eu＝1:1‑x:x:1:4:y:z,0≤x≤1,0.0001≤y≤0.02；0.0001≤z≤0.02；分别称取相应化合物原料，混合均匀后，在氧化性气氛下于1050～1350℃进行高温处理，得到光存储材料。本发明的光存储材料不仅可以存储254nm紫外光，还可以实现对X射线的存储，可应用于X射线、信息存储以及光学防伪等领域。本发明的方法简单，易实现量产。
Description
技术领域
本发明属于长余辉发光材料的技术领域，具体涉及一种LiSc1-xLuxGeO4:Ln3+,Eu3+(Ln＝Tb,Pr,or Bi)光存储材料及其制备方法和应用。
背景技术
随着社会科技的快速发展，每天都在产生大量的数据，如何高效存储与读取所存储的数据成为人们普遍关注的课题。发展新型的光存储材料是解决这个问题的关键。光存储材料是一种无机化合物，通常其由无机化合物晶体的基质、电子陷阱中心与空穴捕获中心所构成。在离化射线，如X射线或高能的254nm紫外光激发下，在光存储材料中能够产生自由的载流子(电子与空穴)。一部分自由载流子能够存储于光存储材料的电子陷阱与空穴陷阱捕获中心。在外界物理刺激下，如650nm红色激光、力或热激励下，存储于陷阱中心的电子或空穴能够被释放。电子与空穴相遇并复合时，所释放的能量能够使复合中心从基态转变到激发态。当复合中心从激发态弛豫回基态时，从而发射出光子。由于这一独特的发光特性，光存储材料已经被运用于X射线成像、信息存储与防伪等领域。
BaFBr(I):Eu2+是一种能够存储X射线的光存储材料，其已被运用于X射线成像技术之中。然而，BaFBr(I):Eu2+存在一些缺点，严重影响了其使用的持久性。首先，BaFBr(I):Eu2 +是含卤素的化合物，其化学稳定性较差。当BaFBr(I):Eu2+暴露于潮湿的空气中，其会大量的吸收空气中的水分，使其结构发生分解。因此，其光存储特性会逐渐失去。因此，如何提高其化学稳定性是一个亟待解决的难题。其次，BaFBr(I):Eu2+在室温时，具有较强的余辉发光特性。存储的载流子会部分以余辉发光的形式释放出来，从而造成存储载流子的损失。BaFBr(I):Eu2+中的陷阱中心来源于材料中的固有缺陷。当前，如何调控固有缺陷来降低室温的余辉发光仍然还不清楚。综上，急需开发化学稳定高及余辉低的新型光存储材料。
发明内容
为了解决现有技术材料的缺陷和不足，本发明公开了一种LiSc1-xLuxGeO4:Ln3+,Eu3 +(Ln＝Tb,Pr,or Bi)光存储材料及其制备方法。本发明的制备方法为高温固相法，合成所需的设备成熟且简单，便于量产化生产。本发明的稀土与铋离子掺杂LiSc1-xLuxGeO4光存储材料具有较高的化学稳定性，载流子存储量高，并且室温的余辉较低。
为了实现以上目的，本发明的技术方案为：
一种LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料，其化学通式为LiSc1-xLuxGeO4:yLn3+,zEu3+；其中，Ln选自Tb、Pr或者Bi，0≤x≤1，0.0001≤y≤0.02，0.0001≤z≤0.02。
可选的，其晶体结构为正交晶系(orthorhombic)，空间群为Pnma(62)。
可选的，其可被X射线或254nm紫外光激发，并产生载流子的存储。
一种上述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料的制备方法，包括以下步骤：
1)根据元素摩尔之比为Li:Sc:Lu:Ge:O:Ln:Eu＝1:1-x:x:1:4:y:z的比例关系，分别称取含各元素的化合物原料；
2)将步骤1)称取的化合物原料混合均匀，在氧化性气氛下于1050～1350℃的温度下进行高温处理，得到所述LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料。
可选的，所述高温处理的保温时间为3～10小时。
可选的，所述高温处理的升温过程是以3～5℃/min的升温速率升温至1050～1350℃，降温过程为随炉自然冷却。
可选的，所述氧化性气氛为氧气气氛或空气气氛。
可选的，所述化合物原料中，
含锂的化合物原料为氧化锂、碳酸锂或氟化锂中的至少一种；
含钪的化合物原料为氧化钪、氟化钪、钪锭或硝酸钪中的至少一种；
含镥化合物原料为氧化镥、氟化镥或无水氯化镥中的至少一种；
含锗的化合物原料为锗粉、氧化锗或碘化锗中的至少一种；
含铽的化合物原料为氧化铽、氯化铽或氟化铽中的至少一种；
含镨的化合物原料为氧化镨、氯化镨或氟化镨中的至少一种；
含铋的化合物原料为铋粉、氧化铋或氯化铋中的至少一种；
含铕的化合物原料为氧化铕、氟化铕、氯化铕或硝酸铕中的至少一种。
上述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料在X射线成像、信息存储或防伪领域中的应用。
本发明的原理如下：化学通式为LiSc1-xLuxGeO4:yLn3+,zEu3+(Ln＝Tb,Pr,或者Bi)的粉末状晶体发光材料。LiSc1-xLuxGeO4为晶体基质，Tb3+、Pr3+或Bi3+为空穴陷阱与发光复合中心，Eu3+为电子陷阱捕获中心。
本发明的有益效果为：
(1)采用理性掺杂的Eu3+为电子捕获中心，而不采用固有缺陷为电子陷阱中心。Eu3 +的电子陷阱深度较深。在室温时，被铕离子捕获的电子释放的量较少，从而有较弱的室温余辉发光。在LiSc1-xLuxGeO4:yLn3+,zEu3+中，Eu3+的电子陷阱深度可以通过调节x的值来进行调控。(2)Bi3+、Tb3+或Pr3+作为空穴陷阱与复合中心，发光颜色可以从紫外光调节到红光区域。LiSc1-xLuxGeO4:yLn3+,zEu3+的化学稳定性高，可被X射线与254nm紫外光有效地激发(charging)，载流子存储量高。
(3)不采用高压和还原性的苛刻合成条件，在常压、氧化性的气氛下，采用高温固相法和LiSc1-xLuxGeO4:yLn3+,zEu3+所需的化学原料即可合成出光存储材料。
(4)本发明的LiSc1-xLuxGeO4:yLn3+,zEu3+光存储材料具有化学稳定性高、载流子存储量高、室温余辉低、可被X射线或254nm紫外光有效激发的独特特性。本发明LiSc1- xLuxGeO4:yLn3+,zEu3+光存储材料的制备条件简单，可批量工业化生产。本发明的光存储材料可应用于X射线、信息存储以及光学防伪等领域。
附图说明
图1为实施例1的配比LiScGeO4:0.003Bi3+,0.001Eu3+，实施例2的LiScGeO4:0.005Pr3+,0.001Eu3+和实施例3的LiScGeO4:0.005Tb3+,0.001Eu3+光存储材料的X射线衍射图谱；
图2为实施例1的配比LiScGeO4:0.003Bi3+,0.001Eu3+光存储材料的余辉发光光谱；
图3为实施例1的配比LiScGeO4:0.003Bi3+,0.001Eu3+光存储材料的热释光光谱；
图4为实施例2的配比LiScGeO4:0.005Pr3+,0.001Eu3+光存储材料的余辉发光光谱；
图5为实施例3的配比LiScGeO4:0.005Tb3+,0.001Eu3+光存储材料的余辉发光光谱；
图6为实施例3的配比LiScGeO4:0.005Tb3+,0.001Eu3+和实施例2的配比LiScGeO4:0.005Pr3+,0.001Eu3+光存储材料的热释光光谱；
图7为实施例4的配比LiLuGeO4:0.005Bi3+,0.001Eu3+，实施例5的LiLuGeO4:0.005Tb3+,0.001Eu3+和实施例6的LiLuGeO4:0.005Pr3+,0.001Eu3+光存储材料的X射线衍射图谱；
图8为实施例7～11的配比LiSc1-xLuxGeO4:0.001Bi3+,0.001Eu3+(x＝0；0.25；0.5；0.75；1)光存储材料的X射线图谱；
图9为实施例7～11的配比LiSc1-xLuxGeO4:0.001Bi3+,0.001Eu3+(x＝0；0.25；0.5；0.75；1)光存储材料的热释光光谱图。
图10为实施例12的配比LiSc0.25Lu0.75GeO4:0.005Tb3+,0.001Eu3+光存储材料用于X射线应用的展示。
具体实施方式
以下结合附图和具体实施例对本发明做进一步解释。本发明的各附图仅为示意以更容易了解本发明，其具体比例可依照设计需求进行调整。
实施例1
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化锗(GeO2)、氧化铋(Bi2O3)和氧化铕(Eu2O3)为原料，按以下配方，根据元素摩尔比称量所需的化合物原料：LiScGeO4:0.003Bi3+,0.001Eu3+；称量好的混合料放入玛瑙研钵中，加入适量的酒精并混合均匀。混合均匀的化合物原料放置于刚玉坩埚之中。坩埚放置于管式炉中，在空气的气氛下，以3℃每分钟的升温速率从25℃升温到1200℃，并在1200℃保持6小时。随后样品随炉子自然冷却至室温。块状样品倒入玛瑙中再次研钵均匀，即可合成晶体化合物光存储材料。
参考图1的X射线衍射图谱。谱图采用日本Rigaku Smar/SmartLa的X射线衍射仪进行采集。谱图采集中，X射线管工作电压设置为40kV和30mA。图1的X射线衍射图谱表明实施例1的LiScGeO4:0.003Bi3+,0.001Eu3+具有LiScGeO4晶体结构(PDF#78-1327)。Bi3+及Eu3+的掺杂并没有引入杂相。
图2为实施例1的配比LiScGeO4:0.003Bi3+,0.001Eu3+光存储材料的余辉发光光谱。激发光源为254nm的汞灯。从图中可以看出，Bi3+的发光为带状，峰值在约350纳米，范围从300纳米到475纳米。Eu3+的发光为线状的发射峰，最强峰值在613纳米，范围在575纳米到650纳米之间。Bi3+的发光强度强于Eu3+的发光强度。余辉发光来源于Bi3+的3P1→1S0和Eu3+的4f→4f特征发光。Bi3+作为空穴捕获与复合中心，Eu3+作为电子捕获中心。Eu3+的4f→4f特征发光来源于Bi3+到Eu3+的能量传递过程。
图3为实施例1的配比LiScGeO4:0.003Bi3+,0.001Eu3+光存储材料的热释光光谱。样品的激发光源为X射线。产生X射线的X射线管工作条件为30kV，50μA和1.5W。样品被X射线激发的温度为300K。样品的升温速率为1K/s。从图中可以看出样品在303K的热释光强度很低。这说明样品的余辉发光很低，存储的载流子能够长时间稳定存储于陷阱中。468K的热释光峰来源于Eu2+电子陷阱中心释放电子。
实施例2
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化锗(GeO2)、氧化镨(Pr6O11)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiScGeO4:0.005Pr3+,0.001Eu3+；称量好的混合料放入玛瑙研钵中，加入适量的酒精并混合均匀。混合均匀的化合物原料放置于刚玉坩埚之中。坩埚放置于管式炉中，在空气的气氛下，以3℃每分钟的升温速率从25℃升温到1200℃，并在1200℃保持6小时。随后样品随炉子自然冷却至室温。块状样品倒入玛瑙中再次研钵均匀，即可合成晶体化合物光存储材料。
图1的X射线衍射图谱表明实施例2的LiScGeO4:0.005Pr3+,0.001Eu3+具有LiScGeO4晶体结构(PDF#78-1327)。Pr3+及Eu3+的掺杂并没有引入杂相。
图4为实施例2的配比LiScGeO4:0.005Pr3+,0.001Eu3+光存储材料的余辉发光光谱。激发光源为254nm的汞灯。从图中可以看出，Pr3+的发光由有多个线状发射峰组成，峰值在～480,602,609,620,642和685纳米。其中，602纳米的发射峰为最强。余辉发光来源于Pr3+的4f→4f特征跃迁发光。Pr3+作为空穴捕获中心与复合发光中心。Eu3+主要作为电子捕获中心。
实施例3
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化锗(GeO2)、氧化铽(Tb4O7)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiScGeO4:0.005Tb3+,0.001Eu3+；称量好的混合料放入玛瑙研钵中，加入适量的酒精并混合均匀。混合均匀的化合物原料放置于刚玉坩埚之中。坩埚放置于管式炉中，在空气的气氛下，以3℃每分钟的升温速率从25℃升温到1200℃，并在1200℃保持6小时。随后样品随炉子自然冷却至室温。块状样品倒入玛瑙中再次研钵均匀，即可合成晶体化合物光存储材料。
图1的X射线衍射图谱表明实施例3的LiScGeO4:0.005Tb3+,0.001Eu3+具有LiScGeO4晶体结构(PDF#78-1327)。Tb3+及Eu3+的掺杂并没有引入杂相。
图5为实施例3的配比LiScGeO4:0.005Tb3+,0.001Eu3+光存储材料的余辉发光光谱。激发光源为254nm的汞灯。从图中可以看出，Tb3+的发光由多个线状发射峰组成。其包含的发射峰值在380,420,438,484,497,542,552,582和620纳米；峰值在552纳米的发射峰为最强。余辉发光来源于Tb3+的特征4f→4f发光。Tb3+是空穴捕获与复合中心，而Eu3+主要作为电子捕获中心。
图6为实施例3的配比LiScGeO4:0.005Tb3+,0.001Eu3+和实施例2的LiScGeO4:0.005Pr3+,0.001Eu3+光存储材料的热释光光谱。样品的激发光源为X射线。测试时，样品的升温速率为1K/s。从图中可以看出样品在303K的热释光强度很低。这说明样品的余辉发光很低，存储的载流子能够长时间稳定存储于陷阱中。峰值在462K和487K热释光峰来源于Eu2+电子陷阱中心释放电子并与Tb4+或Pr4+中的空穴复合。
实施例4
采用碳酸锂(Li2CO3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化铋(Bi2O3)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiLuGeO4:0.005Bi3+,0.001Eu3+；称量好的原料进行混合均匀，装入刚玉坩埚，用刚玉盖子盖住坩埚，刚玉坩埚放入马弗炉中。在空气气氛下，炉子以5℃/分钟的升温速率从室温(25℃)升温到1150℃，炉子在1150℃保温10小时，随后样品随炉冷却到室温，得到光存储材料。
实施例5
采用碳酸锂(Li2CO3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化铽(Tb4O7)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiLuGeO4:0.005Tb3+,0.001Eu3+；称量好的原料进行混合均匀，装入刚玉坩埚，用刚玉盖子盖住坩埚，刚玉坩埚放入马弗炉中。在空气气氛下，炉子以5℃/分钟的升温速率从室温(25℃)升温到1150℃，炉子在1150℃保温10小时，随后样品随炉冷却到室温，得到光存储材料。
实施例6
采用碳酸锂(Li2CO3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化镨(Pr6O11)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiLuGeO4:0.005Pr3+,0.001Eu3+；称量好的原料进行混合均匀，装入刚玉坩埚，用刚玉盖子盖住坩埚，刚玉坩埚放入马弗炉中。在空气气氛下，炉子以5℃/分钟的升温速率从室温(25℃)升温到1150℃，炉子在1150℃保温10小时，随后样品随炉冷却到室温，得到光存储材料。
图7为实施例4的配比LiLuGeO4:0.005Bi3+,0.001Eu3+，实施例5的LiLuGeO4:0.005Tb3+,0.001Eu3+和实施例6的LiLuGeO4:0.005Pr3+,0.001Eu3+光存储晶体材料的X射线衍射图谱。它们的X射线峰为尖锐的线状，这说明所合成的光存储材料的结晶性不错。这些X射线衍射峰与NaLuGeO4(PDF#88-1178)晶体的衍射峰吻合的较好，这说明所合成的光存储材料的晶体结构与NaLuGeO4(PDF#88-1178)相同。Bi3+,Tb3+,Pr3+及Eu3+的掺杂并没有在LiLuGeO4基质中引入杂相。
实施例7
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化锗(GeO2)、氧化铋(Bi2O3)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiScGeO4:0.001Bi3+,0.001Eu3+；原料混合均匀，装入刚玉坩埚。原料与坩埚放入管式炉中。在空气气氛下，炉子以3℃/分钟的升温速率从室温(25℃)升温到1300℃。炉子在1300℃保温8小时，随后样品随炉冷却到室温。块状样品放入玛瑙研钵中研磨成粉状，得到稀土与铋离子掺杂的光存储材料。
实施例8
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化铋(Bi2O3)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiSc0.75Lu0.25GeO4:0.001Bi3+,0.001Eu3+；原料混合均匀，装入刚玉坩埚。原料与坩埚放入管式炉中。在空气气氛下，炉子以3℃/分钟的升温速率从室温(25℃)升温到1300℃。炉子在1300℃保温8小时，随后样品随炉冷却到室温。块状样品放入玛瑙研钵中研磨成粉状，得到稀土与铋离子掺杂的光存储材料。
实施例9
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化铋(Bi2O3)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiSc0.5Lu0.5GeO4:0.001Bi3+,0.001Eu3+；原料混合均匀，装入刚玉坩埚。原料与坩埚放入管式炉中。在空气气氛下，炉子以3℃/分钟的升温速率从室温(25℃)升温到1300℃。炉子在1300℃保温8小时，随后样品随炉冷却到室温。块状样品放入玛瑙研钵中研磨成粉状，得到稀土与铋离子掺杂的光存储材料。
实施例10
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化铋(Bi2O3)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiSc0.25Lu0.75GeO4:0.001Bi3+,0.001Eu3+；原料混合均匀，装入刚玉坩埚。原料与坩埚放入管式炉中。在空气气氛下，炉子以3℃/分钟的升温速率从室温(25℃)升温到1300℃。炉子在1300℃保温8小时，随后样品随炉冷却到室温。块状样品放入玛瑙研钵中研磨成粉状，得到稀土与铋离子掺杂的光存储材料。
实施例11
采用碳酸锂(Li2CO3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化铋(Bi2O3)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiLuGeO4:0.001Bi3+,0.001Eu3+；原料混合均匀，装入刚玉坩埚。原料与坩埚放入管式炉中。在空气气氛下，炉子以3℃/分钟的升温速率从室温(25℃)升温到1300℃。炉子在1300℃保温8小时，随后样品随炉冷却到室温。块状样品放入玛瑙研钵中研磨成粉状，得到稀土与铋离子掺杂的光存储材料。
图8为实施例7～实施例11的配比LiSc1-xLuxGeO4:0.001Bi3+,0.001Eu3+(x＝0；0.25；0.5；0.75；1)光存储材料的X射线图谱。从图中可以看出，LiSc1-xLuxGeO4:0.001Bi3+,0.001Eu3+(x＝0；0.25；0.5；0.75；1)的X射线衍射图谱与标准的LiScGeO4晶体(PDF#78-1327)的衍射峰吻合的很好。这说明，所合成的光存储具有LiScGeO4(PDF#78-1327)的晶体结构。Bi3+与Eu3+的共掺杂并没有引入杂相。
图9为实施例7～实施例11的配比LiSc1-xLuxGeO4:0.001Bi3+,0.001Eu3+(x＝0；0.25；0.5；0.75；1)光存储材料的热释光光谱图。样品的激发光源为X射线。产生X射线的X射线管工作条件为30kV，50μA和1.5W。样品被X射线激发的温度为300K。样品的升温速率为1K/s。从图中可见，说有样品在303K时的热释光强度都很低，这说明样品的室温余辉发光很弱，样品中存储在铕离子中的电子能够稳定的存在。随着x值从1降低到0，Eu2+的热释光峰逐渐从414K增高到460K。在所有样品中，来源于Eu2+的热释光峰为最强。
实施例12
采用碳酸锂(Li2CO3)、氧化钪(Sc2O3)、氧化镥(Lu2O3)、氧化锗(GeO2)、氧化铽(Tb4O7)和氧化铕(Eu2O3)为原料，按以下配方，称量所需的化合物原料：LiSc0.25Lu0.75GeO4:0.005Tb3+,0.001Eu3+；原料混合均匀，装入刚玉坩埚。原料与坩埚放入管式炉中。在空气气氛下，炉子以3℃/分钟的升温速率从室温(25℃)升温到1300℃。炉子在1300℃保温8小时，随后样品随炉冷却到室温。块状样品放入玛瑙研钵中研磨成粉状，得到稀土与铋离子掺杂的光存储材料。
实施例13
实施例1～12的光存储材料应用于X射线、信息存储以及光学防伪等领域。
实施例1～12的光存储材料具有化学稳定性高、载流子存储量高、室温余辉低、可被X射线或254nm紫外光有效激发的独特特性。应用于信息存储领域或X射线成像领域时，如图10(a)所示，可以把实施例12的配方LiSc0.25Lu0.75GeO4:0.005Tb3+,0.001Eu3+的光存储晶体粉末分散于有机树脂中，制备成具有柔性的X射线光存储薄膜。把薄膜放置于检测的物体之下，X射线垂直从上照射薄膜和物体。X照射停止后，把物体从薄膜上取下，薄膜放置于加热台上，并加热到410K，即可得物体的X射线成像照片，如图10(b)。从图中可以看出物体中的被隐藏的金属物质。应用于光学防伪领域时，可以利用实施例1的配比LiScGeO4:0.003Bi3 +,0.001Eu3+，实施例2的LiScGeO4:0.005Pr3+,0.001Eu3+和实施例3的LiScGeO4:0.005Tb3+,0.001Eu3+光存储材料制备成混合发光防伪材料，利用Bi3+,Tb3+与Pr3+不同的发光波长来构成颜色可调的余辉发光，从而实现防伪。
上述实施例仅用来进一步说明本发明的一种LiSc1-xLuxGeO4:Ln3+,Eu3+(Ln＝Tb,Pr,or Bi)光存储材料及其制备方法和应用，但本发明并不局限于实施例，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本发明技术方案的保护范围内。
Claims (9)
1.一种LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料，其特征在于：化学通式为LiSc1-xLuxGeO4:yLn3+,zEu3+；其中，Ln选自Tb、Pr或者 Bi，0≤x≤1，0.0001≤y≤0.02，0.0001≤z≤0.02。
2.根据权利要求1所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料，其特征在于：晶体结构为正交晶系，空间群为Pnma (62)。
3.根据权利要求1所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料，其特征在于：可被X射线或254 nm紫外光激发，并产生载流子的存储。
4.一种权利要求1~3任一项所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料的制备方法，其特征在于，包括以下步骤：
1）根据元素摩尔之比为Li:Sc:Lu:Ge:O:Ln:Eu=1:1-x:x:1:4:y:z的比例关系，分别称取含各元素的化合物原料；
2）将步骤1）称取的化合物原料混合均匀，在氧化性气氛下于1050~1350 oC的温度下进行高温处理，得到所述LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料。
5.根据权利要求4所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料的制备方法，其特征在于：所述高温处理的保温时间为3~10小时。
6.根据权利要求4所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料的制备方法，其特征在于：所述高温处理的升温过程是以3~5 oC/min的升温速率升温至1050~1350 oC，降温过程为随炉自然冷却。
7.根据权利要求4所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料的制备方法，其特征在于：所述氧化性气氛为氧气气氛或空气气氛。
8.根据权利要求4所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料的制备方法，其特征在于：所述化合物原料中，
含锂的化合物原料为氧化锂、碳酸锂或氟化锂中的至少一种；
含钪的化合物原料为氧化钪、氟化钪或硝酸钪中的至少一种；
含镥化合物原料为氧化镥、氟化镥或无水氯化镥中的至少一种；
含锗的化合物原料为氧化锗或碘化锗中的至少一种；
含铽的化合物原料为氧化铽、氯化铽或氟化铽中的至少一种；
含镨的化合物原料为氧化镨、氯化镨或氟化镨中的至少一种；
含铋的化合物原料为氧化铋或氯化铋中的至少一种；
含铕的化合物原料为氧化铕、氟化铕、氯化铕或硝酸铕中的至少一种。
9.权利要求1~3任一项所述的LiSc1-xLuxGeO4:Ln3+,Eu3+光存储材料在X射线成像、信息存储或防伪领域中的应用。
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