CN106430276B - 一种纳米晶及其制备方法和应用 - Google Patents

一种纳米晶及其制备方法和应用 Download PDF

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CN106430276B
CN106430276B CN201610824292.XA CN201610824292A CN106430276B CN 106430276 B CN106430276 B CN 106430276B CN 201610824292 A CN201610824292 A CN 201610824292A CN 106430276 B CN106430276 B CN 106430276B
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雷磊
吴若桢
肖珍
徐时清
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Abstract

本发明涉及无机纳米材料领域。一种纳米晶，化学表达式是Eu/Tb:Gd2O2S。该纳米晶具有依赖激发波长的光学性能，有望应用于防伪标记领域。

Description

一种纳米晶及其制备方法和应用
技术领域
本发明涉及无机纳米材料领域。
背景技术
硫氧化物纳米材料具有低声子能量，无毒性以及高光化学稳定性等特点，被广泛应用于半导体和生物医学领域。以硫氧化物为基质，通过稀土离子掺杂可以实现高效率的荧光性能，例如Tb离子掺杂的纳米晶能够在紫外灯照射下发出明亮的绿光。由于纳米晶的形貌与其光学性能紧密相光，因而实现具有特殊性能的纳米材料的形貌调控具有重要的实际意义。
Tb3+和Eu3+是目前研究非常广泛的两种荧光激活离子，在紫外激发下，Tb3+的发射以绿光为主，Eu3+的发射以红光为主，两者共掺可以实现多色发光。我们在实验中发现，Tb/Eu离子掺杂的纳米晶可以通过改变激发波长来调控其荧光性能，使得这种材料在防伪标记领域具有潜在的应用前景。目前针对稀土硫氧化物纳米材料的形貌调控还鲜见报道，主要是由于这类体系难以通过常规的改变反应温度、时间或者单一离子掺杂等来实现。
发明内容
本发明的一个目的是公开一种具有依赖激发波长的光学性能的纳米晶；本发明的另一个目的是公开一种调控具有依赖激发波长的光学性能的纳米晶形貌的制备方法。
为了实现发明目的，本专利采用了下述的技术方案：
一种纳米晶，化学表达式是Eu/Tb:Gd2O2S。
上述纳米晶的制备方法，在前驱反应液中加入用于改变纳米晶生长过程的Y3+和Sr2+。进一步的，在前驱反应液是乙酰丙酮钆、乙酰丙酮铕、乙酰丙酮铽、油酸和十八烯的混合。进一步的，加入Y3+和Sr2+之后，继续加入硫粉和油胺，且油酸和油胺的比例是1:3，在加入硫粉以后将体系抽真空，纳米晶生长温度高于290℃。
作为优选，上述纳米晶的制备方法包括如下步骤：(1)将(0.48-x)毫摩尔乙酰丙酮钆，0.01毫摩尔乙酰丙酮铕，0.01毫摩尔乙酰丙酮铽，x毫摩尔乙酰丙酮钇，y毫摩尔乙酰丙酮锶，2毫升油酸，8毫升十八烯，在室温下加入到50毫升三颈瓶中，升温至100～150℃，并保温1小时，形成溶液A；(2)待溶液A冷却至50℃以下，加入10毫摩尔硫粉，6毫升油胺，用机械泵将三颈瓶内抽真空约5分钟，然后升温至100～120℃，并保温30分钟，随后在氩气保护条件下，迅速升温至290℃～320℃，并保温1～3小时；(3)待反应液冷却至室温后，加入乙醇离心得到沉淀，并用乙醇：环己烷为3:1的混合液洗涤产物，然后于40℃-80℃烘干后得到最终产物。
作为优选，x是0.05～0.1之间，y是0.2～0.5之间。
一种纳米晶的应用，上述的纳米晶应用于光学防伪标签。
采用以上技术方案的一种纳米晶，具有依赖激发波长的光学性能，有望应用于防伪标记领域。一种纳米晶的制备方法，在前驱溶液中，加入Y3+和Sr2+两种离子，通过改变两种离子的掺杂浓度来改变纳米晶的生长过程，从而得到不同形貌的纳米晶，包括颗粒状、薄片状和花瓣状，这主要归因于：第一，Sr2+取代Gd3+属于异价离子取代，为了使体系达到电荷平衡而在晶格中产生F-空位，而F-空位使得纳米晶表面产生正极朝外的偶极矩，进而加速溶液中F-离子向纳米晶表面扩散，促进纳米晶的生长；第二，Gd3+与Y3+虽然属于同一主族，但是它们具有不同的离子半径，各自具有不同的择优生长取向，使得产物具有不同的形貌。上述纳米晶具有依赖激发波长的光学性能，并且，这种结合多种离子掺杂共同调控纳米晶形貌的方法为制备新颖的纳米材料提供了一个全新的思路。
附图说明
图1：实施例中Tb/Eu：Gd2O2S纳米晶的X射线衍射图；
图2：实施例中Tb/Eu：Gd2O2S纳米晶的透射电镜图；
图3：实施例中Tb/Eu：Gd2O2S纳米晶(x＝0.1，y＝0.5)在不同激发波长条件下的荧光光谱图。
具体实施方式
下面结合图1、图2、图3对本专利实施例做详细的说明。
一种纳米晶，化学表达式是Eu/Tb:Gd2O2S。用于调控Eu/Tb:Gd2O2S纳米晶形貌的制备方法如下步骤：(1)将(0.48-x)毫摩尔乙酰丙酮钆，0.01毫摩尔乙酰丙酮铕，0.01毫摩尔乙酰丙酮铽，x毫摩尔乙酰丙酮钇，y毫摩尔乙酰丙酮锶，2毫升油酸，8毫升十八烯，在室温下加入到50毫升三颈瓶中，升温至150℃，并保温1小时，得到溶液A；(2)待溶液A冷却至50℃以下，加入10毫摩尔硫粉，6毫升油胺，并用机械泵将三颈瓶内抽真空(约5分钟)，然后升温至120℃，并保温30分钟，随后在氩气保护条件下，迅速升温至315℃，并保温1小时；(3)待反应液冷却至室温后，加入乙醇离心得到沉淀，并用乙醇：环己烷为3:1的混合液洗涤产物，然后于60℃烘干后得到最终产物。
图1中a，b，c，d对应不同Y3+和Sr2+离子浓度，分别为(x＝0.05，y＝0.2；x＝0.05，y＝0.5；x＝0.1，y＝0.2；x＝0.1，y＝0.5)，e为标准JCPDS 26-1422卡片。图2中a，b，c，d对应不同Y3+和Sr2+离子浓度，分别为(x＝0.05，y＝0.2；x＝0.05，y＝0.5；x＝0.1，y＝0.2；x＝0.1，y＝0.5)，图中的标尺长度为100nm；图3是纳米晶(x＝0.1，y＝0.5)在不同激发波长条件下的荧光光谱图：(a)234nm(b)254nm(c)274nm(d)294nm(e)314nm(f)334nm(g)365nm。粉末X射线衍射结果表明：所有产物均为纯六方相；透射电镜结果表明：当Y3+和Sr2+离子浓度分别为(x＝0.05，y＝0.2)时，产物为尺寸约为7nm的颗粒状；当Y3+和Sr2+离子浓度分别为(x＝0.05，y＝0.5)时，产物为尺寸约为12nm的颗粒状；当Y3+和Sr2+离子浓度分别为(x＝0.1，y＝0.2)时，产物为尺寸约为47nm的圆片状；当Y3+和Sr2+离子浓度分别为(x＝0.1，y＝0.5)时，产物为花瓣状；光谱结果表明：对于Y3+和Sr2+离子浓度分别为(x＝0.1，y＝0.5)时的Tb/Eu：Gd2O2S纳米晶而言，随着激发波长从234nm逐渐增加到365nm，Tb3+离子的发光强度迅速减弱，而Eu3+离子下降的幅度非常小，导致不同发光波段的比值发生很大变化，并且肉眼可以很清晰的分辨出发光颜色的变化。
传统的光学防伪标签是在某种单一的激发波长下实现的。本专利的光学防伪标签，使用上述的纳米晶，纳米晶能够在不同波长的激发下发射不同颜色的可见光，若将按照特殊的图案镶嵌在标签中，有望制备出新颖的光学防伪标签。

Claims (5)

1.一种纳米晶的制备方法，其特征在于纳米晶化学表达式是Eu/Tb: Gd2O2S；在前驱反应液中加入用于改变纳米晶生长过程的Y3+和Sr2+；加入Y3+和Sr2+之后，继续加入硫粉和油胺，在加入硫粉以后将体系抽真空，纳米晶生长温度高于290 ℃。
2.根据权利要求1所述的一种纳米晶的制备方法，其特征在于在前驱反应液是乙酰丙酮钆、乙酰丙酮铕、乙酰丙酮铽、油酸和十八烯的混合。
3.根据权利要求2所述的一种纳米晶的制备方法，其特征在于油酸和油胺的比例是1:3。
4.根据权利要求1所述的一种纳米晶的制备方法，其特征在于包括如下步骤：（1）将（0.48-x）毫摩尔乙酰丙酮钆，0.01毫摩尔乙酰丙酮铕，0.01毫摩尔乙酰丙酮铽，x毫摩尔乙酰丙酮钇，y毫摩尔乙酰丙酮锶，2毫升油酸，8毫升十八烯，在室温下加入到50毫升三颈瓶中，升温至100～150oC，并保温1小时，形成溶液A；（2）待溶液A冷却至50oC以下，加入10毫摩尔硫粉，6毫升油胺，用机械泵将三颈瓶内抽真空约5分钟，然后升温至100～120o C ，并保温30分钟，随后在氩气保护条件下，迅速升温至290o C～320o C，并保温1～3小时；（3）待反应液冷却至室温后，加入乙醇离心得到沉淀，并用乙醇：环己烷为3:1的混合液洗涤产物，然后于40o C-80o C烘干后得到最终产物。
5.根据权利要求4所述的一种纳米晶的制备方法，其特征在于x是0.05～0.1，y是0.2～0.5。
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