CN106753367A - 一种稀土离子掺杂的卤铅酸铋半导体发光材料 - Google Patents
一种稀土离子掺杂的卤铅酸铋半导体发光材料 Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 29
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- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
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- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
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- 239000000460 chlorine Substances 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 18
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 6
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- 239000013078 crystal Substances 0.000 description 4
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- 238000000034 method Methods 0.000 description 4
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- 239000002253 acid Substances 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
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- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7701—Chalogenides
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- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
本发明提供一种稀土离子掺杂的卤铅酸铋半导体发光材料,其化学式为Bi1‑yReyPbO2X;其中,y=0.001~0.4,X为F、Cl、Br、I中的一种或任意几种,Re为Tb、Ce、Nd、Dy、Eu、Sm、Pr、Lu、Er、Tm、Yb、Gd中的一种或任意几种;本发明提供的稀土离子掺杂的卤铅酸铋半导体发光材料具有很好的发光性质,且物理化学性质稳定,制备方法简单、原材料成本低;该材料有望作为新型紫外、可见、近红外发光材料得到应用。
Description
技术领域
本发明涉及稀土离子掺杂半导体发光材料,具体涉及一种可在紫外光、可见光以及近红外光激发下具有发光性能的稀土离子掺杂的卤铅酸铋半导体发光材料。
背景技术
宽带隙半导体对紫外和可见光具有很好的吸收能力,其可以自身作为发光材料,同时还可以与稀土光激活离子结合。当作为稀土掺杂离子的基质材料时,半导体的光物理性质和稀土离子光学性能有可能结合,从而获得优异而丰富的发光性能。例如稀土掺杂卤氧化铋BiOX (X =F、 Cl、Br或I)半导体具有优异的发光性能;一个重要的原因在于,BiOCl除了较低的声子能量,还容易形成层状结构,在晶体中的[Bi2O2]阳离子层与Cl-阴离子层之间可以形成极化内电场;当稀土离子掺入到BiOCl中时,这种晶体内部的自极化电场可以有效促进稀土离子的发光效率。然而卤氧化铋晶体中,其表层原子的Bi-O键合力相对较弱,在合成过程中以及长期暴露于紫外光照射下容易氧缺陷;当卤氧化铋作为半导体光催化剂时,这种表面氧缺陷反而可以促进光化学反应的进行;然而当卤氧化铋作为长期使用的发光材料时,大量表面氧缺陷的存在会导致稀土离子的荧光出现猝灭,会带来不利影响;为了改善这种氧缺陷对BiOCl的影响,当作为珠光颜料时,研究人员曾采用CeO2来包裹BiOCl吸收紫外线,以提高其稳定性;然而这类方法成本相对价高,同时会消耗大量昂贵的稀土资源。
发明内容
本发明的目的在于针对现有卤氧化铋BiOX (X =F、Cl、Br或I)半导体发光材料的容易形成表面氧缺陷的不足,提供一种物理和化学性质更加稳定的卤铅酸铋半导体发光材料;卤铅酸铋也是一种层状结构半导体,其结构与BiOCl有一定的相似性,不同的是PbO与[Bi2O2]结合形成了[PbBi2O3]阳离子层;当PbO组分引入到卤氧化铋结构中后,由于Pb与Bi相似都属于重金属元素区,都有相对较低的声子能量,有利于稀土的发光;同时Pb2+有着Bi3 +离子更高的电负性和极化率,与其他组分或者元素引入该体系不同,PbO组分的引入,由于阳离子组分电负性的提高,可以有效的提高与晶体中O的结合力,提高材料的化学和物理稳定性,避免和减少了表面氧缺陷的形成;另外,PbO结构的引入还可以进一步促进极化内电场的形成,提高稀土离子的发光效率,并改变稀土离子的发光行为,得到不同于普通材料的发光现象。
本发明提出的稀土离子掺杂卤铅酸铋半导体发光材料,其化学式为Bi1-yReyPbO2X;其中,y=0.001~0.4,X为F、Cl、Br、I中的一种或任意几种,Re为Tb、Ce、Nd、Dy、Eu、Sm、Pr、Lu、Er、Tm、Yb、Gd中的一种或任意几种。
本发明上述稀土离子掺杂的卤铅酸铋半导体发光材料,经过下列各步骤获得:
(1)按Bi离子︰Re离子︰Pb离子︰卤素离子的摩尔比=1-y︰y︰1︰1,以硝酸铋、稀土硝酸盐、硝酸铅或者卤铅酸、卤盐(卤化钾、卤化钠或者卤化铵)为原料,溶解于水或者有机溶剂(乙醇、甲醇、乙二醇、乙酸乙酯中一种)中,或者溶解于水与有机溶剂形成的混合液中,分别配置成摩尔浓度为0.1~2 mol/L的溶液;然后将上述溶液搅拌均匀,用盐酸以及氨水调节pH值至2~9,然后转入带有聚四氟乙烯内衬的水热釜中,装填度为0.4~0.8,然后升温至110~250℃,保温2~30小时;
(2)将步骤(1)所得物料用去离子水、乙醇洗涤各三次,烘干;也可对烘干产物进一步在200~800℃下热处理0.5~4小时,即得到化学式为Bi1-yReyPbO2X的稀土离子掺杂卤铅酸铋半导体发光材料。
或者采用下述方法获得:
1)按Bi离子︰Re离子︰Pb离子︰卤素离子的摩尔比=1-y︰y︰1︰1,以氧化铋、稀土氧化物、氧化铅和卤化铅、卤化铵为原料;其中卤化铵按照上述配比基础上再过量5~40 mol%,以弥补这类物质在高温固相合成过程中产生的挥发;将上述原料研磨混合均匀后,放置于坩埚中,在坩埚表面加盖并在300~800℃条件下烧结1~6小时,冷却至室温,然后用去离子水或者乙醇洗去多余的卤化铵,烘干后制得化合物。
本发明与现有的稀土离子掺杂卤氧化铋半导体材料以及现有常规稀土掺杂荧光粉材料相比,具有如下突出的优点:制备方法简单、高温固相法合成温度低,使用过程中尤其紫外光照射下物理化学性能更加稳定, 同时还能得到不同于传统稀土发光材料的荧光性质,该材料有望作为新型紫外、可见、及近红外荧光材料以及生物探针材料中得到应用。
附图说明
图1是固相法制备的Bi0.99Eu0.01PbO2Cl材料的发射荧光光谱;
图2是固相法制备的Bi0.99Eu0.01PbO2Cl材料的激发光谱。
具体实施方式
下面将结合实施例进一步阐明本发明的内容,但本发明的保护范围并不局限于这些实施例。
实施例1:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.999Er0.001PbO2Cl;该材料制备方法如下:
(1)按Bi离子︰Er离子︰Pb离子︰Cl离子的摩尔比=0.999︰0.001︰1︰1,以Bi(NO3)3.5H2O、Er(NO3)3、Pb(NO3)2、KCl为原料,分别溶解于水中分别配成成浓度为0.1mol/L的溶液;然后将上述溶液加入容器中搅拌混合均匀,并用浓度为1mol/L的盐酸调节pH值为1,然后转入带有聚四氟乙烯内衬的水热釜中,装填度为0.4,然后升温至120℃,保温12小时;
(2)将步骤(1)所得物料用去离子水、乙醇分别洗涤三次,烘干,即得到化学组成式为Bi0.999Er0.001 PbO2Cl的稀土Er离子掺杂氯铅酸铋半导体发光材料,该材料在紫外光照射下性能稳定,当采用近红外光激发时可以得到不同于Er掺杂传统发光材料的光子雪崩现象。
实施例2:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.95Tm0.01 Yb0.04PbO2Cl;该材料制备方法如下:
(1)按Bi离子︰(Tm离子+Yb离子)︰Pb离子︰Cl离子=0.95︰(0.01+0.04)︰1︰1,以Bi(NO3)3.5H2O、Tm(NO3)3、Yb(NO3)3、Pb(NO3)2、NaCl为原料,分别溶解于乙醇溶液中分别配置成浓度为0.5mol/L的溶液,然后将上述溶液加入容器中搅拌混合均匀,并用浓度为0.5mol/L的盐酸调节pH值为4,然后转入带有聚四氟乙烯内衬的水热釜中,装填度为0.6,然后升温至160℃,保温12小时;
(2)将步骤(1)所得物料用去离子水、乙醇洗涤各洗涤三次,烘干,然后在500℃条件下热处理2小时,即得到化学式为Bi0.95Tm0.01 Yb0.04 PbO2Cl的稀土离子掺杂氯铅酸铋发光材料,该材料在紫外光照射下性能稳定,当采用近红外光激发时可以得到不同于Tm掺杂传统发光材料的短波近红外发光性质。
实施例3:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.9Dy0.1 PbO2Cl;该材料制备方法如下:
(1)按Bi离子︰Dy离子︰Pb离子︰Cl离子的摩尔比=0.9︰0.1︰1︰1,以BiCl、Dy(NO3)3、Pb(NO3)2、NH4Cl为原料,溶解乙二醇中分别配制成浓度为0.8mol/L的溶液,将上述溶液混合搅拌搅拌均匀,用浓度为2mol/L的氨水调节pH值为6,然后继续搅拌12小时;
(2)将步骤(1)所得物料用去离子水、乙醇洗涤各三次,烘干,然后在500℃条件下热处理2小时,即得到化学组成式为Bi0.9Dy0.1 PbO2Cl的稀土离子掺杂氯铅酸铋半导体发光材料,该材料在紫外光照射下性能稳定,紫外激发下可以得到较强的白光发射。
实施例4:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.9Pr0.1 PbO2I;该材料制备方法如下:
1)按Bi离子︰Pr离子︰Pb离子︰I离子的摩尔比=0.9︰0.1︰1︰1,以Bi(NO3)3.5H2O、Pr(NO3)3、Pb(NO3)2、KI为原料,溶解乙二醇分别配制成浓度为0.8mol/L的溶液;将上述溶液搅拌均匀,并用浓度为0.5mol/L的盐酸调节pH值为6,然后继续搅拌12小时;
(2)将步骤(1)所得物料用去离子水、乙醇洗涤各三次,烘干,然后在500℃条件下热处理2小时,即得到化学组成式为Bi0.9Pr0.1PbO2I的稀土离子掺杂碘铅酸铋半导体发光材料,该材料在紫外光照射下性能稳定,紫外激发下可以得到Eu3+离子的远红外发射。
实施例5:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.8Nd0.1Ce0.1PbO2Cl;该材料制备方法如下:
(1)按Bi离子︰(Nd离子+Ce离子): Pb离子︰Cl离子的摩尔比=0.8︰(0.1+0.1)︰1︰1,以Bi(NO3)3.5H2O、Pb(NO3)2、Nd(NO3)3、Ce(NO3)3、KCl为原料,溶解于甲醇中,配制成浓度为1mol/L的溶液,用盐酸调节pH值为6,然后转入带有聚四氟乙烯内衬的水热釜中,装填度为0.8,然后升温至180℃,保温6小时;
(2)将步骤(1)所得物料用去离子水、乙醇洗涤各三次,烘干,然后在400℃条件下热处理2小时,即得到化学组成式为Bi0.8Nd0.1Ce0.1PbO2Cl的稀土离子掺杂氯铅酸铋半导体发光材料,该材料在紫外光照射下性能稳定,紫外激发下可以得到Ce3+离子较强的紫光发射。
实施例6:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.8Tb0.1Lu0.1PbO2Cl0.5Br0.5;该材料制备方法如下:
(1)按Bi离子︰(Tb离子+Lu离子)︰Pb离子︰(Cl+Br)离子的摩尔比=0.8︰(0.1+0.1)︰1︰(0.5+0.5),以Bi(NO3)3.5H2O、Tb(NO3)3、Lu(NO3)3,Pb(NO3)2、KCl、KBr为原料,溶解于水配置成配制成浓度为1.2mol/L,并用浓度为0.5mol/L的盐酸调节pH值为5,然后转入带有聚四氟乙烯内衬的水热釜中,装填度为0.8,然后升温至200℃,保温4小时;
(2)将步骤(1)所得物料用去离子水、乙醇洗涤各三次,烘干,然后在500℃条件下热处理2小时,即得到化学组成式为Bi0.8Tb0.1Lu0.1PbO2Cl0.5Br0.5的稀土离子掺杂卤铅酸铋半导体发光材料,该材料在紫外光照射下性能稳定,紫外激发下可以得到Tb3+离子较强的绿光发射。
实施例7:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.6Tm0.2Yb0.2PbO2I;该材料制备方法如下:
(1)按Bi离子︰(Tm离子+Yb离子)︰Pb离子︰I离子的摩尔比=0.6︰0.2︰0.2︰1︰1,以Bi(NO3)3.5H2O、Tm(NO3)3、Yb(NO3)3、Pb(NO3)2、KI为原料,溶解于甲醇中配制成浓度为2mol/L,用浓度为2mol/L的氨水调节为10,然后转入带有聚四氟乙烯内衬的水热釜中,装填度为0.8,然后升温至220℃,保温2小时;
(2)将步骤(1)所得物料用去离子水、乙醇洗涤各三次,烘干,即得到化学组成式为Bi0.6Tm0.2Yb0.2 PbO2I的稀土离子掺杂碘铅酸铋半导体发光材料,该材料在紫外光照射下性能稳定,当采用近红外光激发时可以得到不同于Tm掺杂传统发光材料的短波近红外发光性质。
实施例8:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.7Er0.15Gd0.15PbO2Cl;该材料制备方法如下:
(1)按Bi︰(Er离子+Gd离子)︰Pb离子︰Cl︰的摩尔比=0.7︰(0.15+0.15)︰1︰1,称取Bi2O3、Er2O3、Gd2O3、PbCl2、NH4Cl共50g,其中NH4Cl称量是比理论值多称5 mol%,并将上述物料混合均匀;
(2)将步骤(1)所得混合料装入坩埚加盖,然后升温至800℃,再保温3小时后随炉温冷却,用去离子水洗去多余的氯化铵,烘干后即得到化学式为Bi0.7Er0.15Gd0.15PbO2Cl的稀土掺杂氯铅酸铋半导体发光材料,该材料在紫外光照射下性能稳定,紫外激发下可以得到Er3+离子较强的绿光发射。
实施例9:本稀土离子掺杂卤铅酸铋半导体发光材料化学式为Bi0.92Sm0.08PbO2F0.8Br0.2;该材料制备方法如下:
(1)按Bi︰Sm离子:Pb离子:(F+Br)的摩尔比=0.92︰0.08︰1︰(0.8+0.2),称取Bi2O3、Sm2O3、PbO、NH4F、NH4Br共50g,其中NH4Br称量是比理论值多称40 mol%,NH4F称量是比理论值多称40mol%,并将上述物料混合均匀;
(2)将步骤(1)所得混合料装入坩埚加盖,然后升温至400℃,再保温6小时后随炉温冷却,用去乙醇洗去多余的氟化铵和溴化铵,烘干后即得到化学组成式为Bi0.92Sm0.08PbO2F0.8Br0.2的稀土掺杂卤铅酸铋半导体荧光材料,该材料在紫外光照射下性能稳定,紫外激发下可以得到Sm3+离子较强的红光发射。
实施例10:本稀土离子掺杂卤铅酸铋发光材料化学式为Bi0.99Eu0.01 PbO2Cl;该材料制备方法如下:
(1)按Bi︰Eu离子:Pb离子:Cl的摩尔比=0.99︰0.01︰1︰1,称取Bi2O3、Eu2O3、PbO、NH4Cl共50g,其中NH4Cl称量是比理论值多称30 mol%,并将上述物料混合均匀;
(2)将步骤(1)所得混合料装入坩埚加盖,然后升温至600℃,再保温6小时后随炉温冷却,用去乙醇洗去多余的NH4Cl,烘干后即得到化学组成式为Bi0.99Eu0.01PbO2Cl的稀土掺杂卤铅酸铋半导体发光材料;这类材料不生不同于传统Eu3+掺杂发光材料,该材料在紫外光照射下性能稳定,激发下可以得到Eu3+离子位于698 nm较强的远红光发射(见图1),该性质可以在生物及农业方面具有应用;另外该材料的Eu3+荧光发射在紫外波段具有较强的宽带激发特性,激发效率高,可激发范围宽,在紫外激发的荧光材料中具有很好的应用(见图2)。
Claims (1)
1.一种稀土离子掺杂的卤铅酸铋半导体发光材料,其特征在于:化学式为Bi1- yReyPbO2X;其中,y=0.001~0.4,X为F、Cl、Br、I中的一种或任意几种,Re为Tb、Ce、Nd、Dy、Eu、Sm、Pr、Lu、Er、Tm、Yb、Gd中的一种或任意几种。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109794271A (zh) * | 2019-01-28 | 2019-05-24 | 江苏大学 | 一种富氧缺陷超薄PbBiO2Br纳米片的制备方法及其用途 |
CN111354846A (zh) * | 2020-04-28 | 2020-06-30 | 东莞市索菲电子科技有限公司 | 一种高显色指数的led荧光粉配方及其制备方法 |
CN113683056A (zh) * | 2020-05-19 | 2021-11-23 | 中国科学院上海硅酸盐研究所 | 一种光催化制备氯气的方法 |
CN113755170A (zh) * | 2021-10-11 | 2021-12-07 | 江西乾照光电有限公司 | 一种稀土离子掺杂硅酸铋上转换发光材料及其制备方法 |
CN113786850A (zh) * | 2021-10-14 | 2021-12-14 | 昆明理工大学 | 一种光催化剂及其制备方法和应用 |
-
2017
- 2017-01-16 CN CN201710028500.XA patent/CN106753367B/zh active Active
Non-Patent Citations (3)
Title |
---|
WEIWEI WU: "Near-single-band red upconversion luminescence in Yb/Er: BiOX (X = Cl, Br) nanoplatelets", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
WENWU ZHONG: "Synthesis and structure of BiPbO2Cl nanosheet with enhanced visible light photocatalytic activity", 《APPLIED SURFACE SCIENCE》 * |
洪广言、庄卫东: "《稀土发光材料》", 31 May 2016, 冶金工业出版社 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109794271A (zh) * | 2019-01-28 | 2019-05-24 | 江苏大学 | 一种富氧缺陷超薄PbBiO2Br纳米片的制备方法及其用途 |
CN109794271B (zh) * | 2019-01-28 | 2021-09-10 | 江苏大学 | 一种富氧缺陷超薄PbBiO2Br纳米片的制备方法及其用途 |
CN111354846A (zh) * | 2020-04-28 | 2020-06-30 | 东莞市索菲电子科技有限公司 | 一种高显色指数的led荧光粉配方及其制备方法 |
CN111354846B (zh) * | 2020-04-28 | 2021-04-23 | 东莞市索菲电子科技有限公司 | 一种高显色指数的led荧光粉配方及其制备方法 |
CN113683056A (zh) * | 2020-05-19 | 2021-11-23 | 中国科学院上海硅酸盐研究所 | 一种光催化制备氯气的方法 |
CN113755170A (zh) * | 2021-10-11 | 2021-12-07 | 江西乾照光电有限公司 | 一种稀土离子掺杂硅酸铋上转换发光材料及其制备方法 |
CN113755170B (zh) * | 2021-10-11 | 2023-09-15 | 江西乾照光电有限公司 | 一种稀土离子掺杂硅酸铋上转换发光材料及其制备方法 |
CN113786850A (zh) * | 2021-10-14 | 2021-12-14 | 昆明理工大学 | 一种光催化剂及其制备方法和应用 |
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