CN113130696B - 基于量子限制斯塔克效应的光开关 - Google Patents

基于量子限制斯塔克效应的光开关 Download PDF

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CN113130696B
CN113130696B CN202110403020.3A CN202110403020A CN113130696B CN 113130696 B CN113130696 B CN 113130696B CN 202110403020 A CN202110403020 A CN 202110403020A CN 113130696 B CN113130696 B CN 113130696B
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张家雨
陈伟敏
项文斌
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Abstract

一种基于量子限制斯塔克效应的光开关，其特征在于，在石英衬底上刻蚀交叉指型电极，交叉电极之间沉积有序取向的II‑VI族半导体纳米片(NPLs)层，其中主要通过液‑液界面自组装，控制油酸/二甘醇(OA/DEG)溶液中油酸的比例，使得纳米片面朝下，两侧边缘分别朝向正负电极，从而增强量子限制斯塔克效应，实现光开关的高对比度。本发明是基于量子限制斯塔克效应的全光开关，设计原理清晰，结构简单，偏振无依赖，高开关比，实现高性能光开关。

Description

基于量子限制斯塔克效应的光开关
技术领域
本发明属于光电开关技术领域，尤其是一种基于量子限制斯塔克效应的光开关。
背景技术
信息互联网时代的飞速发展，对光通信技术的信息存储、传输速率、可靠性提出了更高的要求。光开关作为集成光学系统基本单元器件之一，在芯片内的信息互连、数据远距离传输、网络之间的光信号交换等领域发挥十分重要的作用。此外，光开关还是实现光子计算机和量子计算机的基石，它的性能往往决定了整个系统性能的上限。因此，实现具有高速率、低功耗、高对比度、小尺寸等特性的高性能光开关至关重要。目前，这些光开关大多采用电光控制的光开关，网络中的各个节点频繁的光/电和电/光转换，存在串话、高损耗、传输速率受限等缺点。实现全光开关，即光控开光，是实现全光信号处理技术，突破“电子瓶颈”的重要基本单元器件，在通讯网络中具有很大的价值应用。
随着工业生产对于器件集成度需求的提升,以普通三维材料为基础的器件已经难以达到应用要求,低维半导体器件的兴起将有望解决这个问题。许多低维半导体纳米材料由于特殊的空间结构，能级分布在特定波段发生显著的非线性光学变化，从而广泛应用于非线性光学领域。准零维量子点材料、准一维纳米线材料和二维纳米材料都存在一系列丰富的相关特性。其中，量子限制斯塔克效应的物理起源是在外电场的作用下，量子阱结构中电子-空穴之间的库仑力相互作用形成内建电场，在内外电场共同作用下，导致能带结构的畸变，吸收边移动等现象。基于量子限制斯塔克效应的量子点非线性光开关行为，具有皮秒量级的开关时间，并且不受输入光信号的偏振模式影响。但是基于量子点的全光开关，对于光的滤波效果不显著，光开关比不大，可靠性降低。
发明内容
本发明要解决的技术问题是现有量子点光开关的缺点和不足，提出了一种基于量子限制斯塔克效应的光开关。该光开关为纳米片，开关调制深度优于基于量子点的光开关的调制深度，且具有高开关比、偏振无依赖、结构简单等特性。
本发明的一种基于量子限制斯塔克效应的光开关的制备方法，其特征在于，具体包括如下步骤：
步骤1，在石英衬底上刻蚀交叉指型电极；
对石英衬底烘烤脱水，在石英衬底上涂光刻胶，用掩膜版挡住衬底进行曝光、显影，用高真空镀膜机镀镀多金属膜；清洗掉光刻胶得到周期性的电极结构，即交叉指型电极，交叉指型电极的两侧有金属线引出端，用于连接外部电压的正负极。
步骤2，在交叉电极之间沉积有序取向的II-VI族半导体纳米片(NPLs)层，所述II-VI族半导体纳米片为CdSe/CdS纳米片，且为核/壳异质结构的CdSe/CdS纳米片。
进一步的，步骤2中核/壳异质结构的CdSe/CdS纳米片的制备过过程如下：
步骤2.1，CdSe核纳米片的制备；
Se前驱体的制备：粉和十八烯加入玻璃瓶中；用聚四氟乙烯塞封口密封，超声后得到Se粉悬浊液体。
Cd前驱体的制备：氧化镉、油酸和十八烯加入三口烧瓶；磁力搅拌的条件下，通入氩气进行鼓泡除气，升温至240℃，直至溶液从浑浊变成无色透明，再降温至60℃；将透明前驱体溶液转移至玻璃取样瓶中，用聚四氟乙烯塞封口密封，通入氩气除气。
S前驱体的制备：辛硫醇和十八烯加入玻璃取样瓶；用聚四氟乙烯塞封口密封，通入氩气除气，摇晃使充分混合。
将氧化镉、十四酸、十八烯加入三口烧瓶；磁力搅拌的条件下，通入氩气进行鼓泡除气，在110℃温度下除气30min；继续升温至285℃，直至溶液无色透明，再降温至90℃；注入Se前驱体溶液，再次除气；升温至195℃时，加入醋酸镉；继续升温至240℃，反应得到CdSe核纳米片；快速降至室温，当温度降至180℃时注入油酸；用正己烷-乙醇混合溶液离心提纯，最后将沉淀分散在正己烷中。
步骤2.2，CdSe/CdS核/壳纳米片的制备
取CdSe纳米片、Cd前驱体溶液和十八烯加入三口烧瓶；磁力搅拌的条件下，通入氩气鼓泡除气，室温除气40min；升温至80℃继续除气20min；在氩气保护下，设置300℃升温；温度升至180℃时，注入油胺。同时，硫前驱通过注射泵开始注入，速度为3mL h-1；前驱体注入完成后，保持在300℃退火10min；冷却至室温，在温度降至240℃时加入正己烷，降温至180℃时加入油酸；用甲醇进行原位提纯两次，去除溶液中过多的十八烯；加入正己烷-乙醇混合溶液离心提纯，将制备好的CdSe/CdS核/壳纳米片分散在正己烷中。
进一步的，步骤2中在交叉电极之间沉积有序取向的II-VI族半导体纳米片(NPLs)层，具体为：
1)在聚四氟乙烯井内放置上交叉电极作为基板；
2)将油酸/二甘醇(OA/DEG)溶液加入井中，然后加入CdSe/CdS核/壳纳米片正己烷溶液；
3)用玻璃培养皿覆盖聚四氟乙烯井以减慢正己烷蒸发的速度；
4)己烷溶剂完全蒸发后，缓慢排出二甘醇DEG，使自组装膜沉积在基质上，纳米片面朝下，两侧边缘分别朝向正负电极。
有益效果：基于量子限制斯塔克效应，通过控制CdSe/CdS核/壳纳米片有序取向，实现高性能的全光开关。胶体半导体纳米片具有与量子阱类似的电子结构，且其光学性能可以在核/壳异质结构中进一步提升。控制纳米片有序取向，让纳米片面朝下，其中两侧边缘分别朝向正负电极，在外电场的作用下，荧光光谱相较于量子点的光谱移动红移的更多，此时对于输入光信号的自然展宽，在实现“关”这个功能下，透过率大大降低，从而实现了高对比度的光开关。本发明是基于量子限制斯塔克效应的全光开关，设计原理清晰，结构简单，偏振无依赖，高开关比，对于低维材料的非线性光学特性在光学元器件，光通信领域具有重要意义。
附图说明
图1为本发明的器件电极结构图。
图2为聚四氟乙烯井图。
其中1、交叉指型电极；2、CdSe/CdS纳米片；3、聚四氟乙烯井中。
具体实施方式
本发明的一种基于量子限制斯塔克效应的光开关的制备方法，具体包括如下步骤：
步骤1，在石英衬底上刻蚀交叉指型电极1，电极间距在几个微米量级；具体为：
对石英衬底以150～200℃烘烤的温度脱水烘烤，在石英衬底上涂一层负性su8光刻胶，厚度约为2μm；软烤，去除光刻胶中的大部分溶剂并使胶的曝光特性固定，软烤温度是90～100℃，时间为10min；用掩膜版挡住衬底进行曝光；曝光后烘烤，激活曝光后的光刻胶化学性能，温度为90℃，时间为5min；显影，浸泡在浓度为5％的NaOH溶液，通过控制浸泡时间控制显影程度；硬烤，在真空或干燥氮气的气氛中，以150～200℃烘烤，去除残余显影液和蒸馏水；用高真空镀膜机镀上一层厚度为2μm的Au；用丙酮等光刻胶清洗液浸泡已镀Au的石英片，去除su-8及其上面的Au得到周期性的电极结构，即交叉指型电极1，交叉指型电极1的两侧有金属线引出端，用于连接外部电压的正负极，如图1所示。
步骤2，在交叉电极之间沉积有序取向的II-VI族半导体纳米片(NPLs)层，所述II-VI族半导体纳米片为CdSe/CdS纳米片2，且为核/壳异质结构，具体为包括如下步骤：
步骤2.1，CdSe核纳米片(4MLs)的制备
Se前驱体的制备：180mg Se粉和15mL十八烯加入20mL玻璃瓶；用聚四氟乙烯塞封口密封，超声30min,得到Se粉悬浊液体。
Cd前驱体的制备：0.51364g氧化镉、2.51g油酸和40mL十八烯加入100mL三口烧瓶；磁力搅拌的条件下，通入氩气进行鼓泡除气，在80℃温度下除气30min；升温至240℃，直至溶液从浑浊变成无色透明，再降温至60℃；将透明前驱体溶液转移至40mL的玻璃取样瓶中，用聚四氟乙烯塞封口密封，通入氩气除气10分钟。
S前驱体的制备：252μL辛硫醇和36mL十八烯加入40mL的玻璃取样瓶；用聚四氟乙烯塞封口密封，通入氩气除气10min；摇晃10min使充分混合。
将70mg氧化镉、340mg十四酸、28mL十八烯加入100mL三口烧瓶；磁力搅拌的条件下，通入氩气进行鼓泡除气，在110℃温度下除气30min；继续升温至285℃，直至溶液无色透明，再降温至90℃；注入2mL的Se前驱体溶液，再次除气；升温至195℃时，加入160mg醋酸镉；继续升温至240℃，反应10min,得到CdSe核纳米片；快速降至室温，当温度降至180℃时注入1mL油酸；将原溶液分成两管，用20mL正己烷-乙醇混合溶液(3:1)离心提纯，最后将制成的CdSe核纳米片分散在正己烷中。
步骤2.2，CdSe/CdS核/壳纳米片的制备
取上述一半CdSe纳米片、2.15mLCd前驱体溶液和3mL十八烯加入50mL三口烧瓶；磁力搅拌的条件下，通入氩气鼓泡除气，室温除气40min；升温至80℃继续除气20min；在氩气保护下，设置300℃升温；温度升至180℃时，注入1mL油胺。同时，硫前驱通过注射泵开始注入，速度为3mL h-1；前驱体注入完成后，保持在300℃退火10min；用湿毛巾冷却至室温，在温度降至240℃时加入5mL正己烷，降温至180℃时加入1mL油酸；用甲醇进行原位提纯两次，去除溶液中过多的十八烯；加入正己烷-乙醇混合溶液离心提纯，将制备好的CdSe/CdS核/壳纳米片分散在正己烷中，每个CdSe/CdS核/壳纳米片中含有4个单层的CdSe核纳米片(～1.4nm)。
步骤2.3交叉指型电极1放入聚四氟乙烯井3的方形槽内，加入CdSe/CdS核/壳纳米片正己烷溶液，通过液-液界面自组装控制纳米晶体取向。
在聚四氟乙烯井3中放置上述制备的交叉指型电极1作为基板，聚四氟乙烯井3为3mm×3mm大小的方形槽，井的底部有一个排水孔，如图2所示；将约2.4mL的油酸(4.2mM)/二甘醇(OA/DEG)溶液加入井中，然后从顶部加入上述制备的CdSe/CdS核/壳纳米片正己烷溶液；用玻璃培养皿覆盖聚四氟乙烯井3以减慢正己烷蒸发的速度；己烷溶剂完全蒸发后，缓慢排出二甘醇DEG，使自组装膜沉积在基质上，其中纳米片面朝下，两侧边缘分别朝向正负电极。

Claims (5)

1.一种基于量子限制斯塔克效应的光开关的制备方法，其特征在于，具体包括如下步骤：
步骤1，在石英衬底上刻蚀交叉指型电极；
步骤2，在交叉电极之间沉积有序取向的II-VI族半导体纳米片NPLs层，所述有序取向是指纳米片面朝下，其中两侧边缘分别朝向正负电极，所述II-VI族半导体纳米片为CdSe/CdS纳米片，且为核/壳异质结构的CdSe/CdS纳米片。
2.根据权利要求1所述一种基于量子限制斯塔克效应的光开关的制备方法，其特征在于，步骤1中在石英衬底上刻蚀交叉指型电极，具体过程为：
对石英衬底烘烤脱水，在石英衬底上涂光刻胶，用掩膜版挡住衬底进行曝光、显影，用高真空镀膜机镀金属膜；清洗掉光刻胶得到周期性的电极结构，即交叉指型电极，交叉指型电极的两侧有金属线引出端，用于连接外部电压的正负极。
3.根据权利要求1所述一种基于量子限制斯塔克效应的光开关的制备方法，其特征在于，步骤2中核/壳异质结构的CdSe/CdS纳米片的制备过程如下：
步骤2.1，CdSe核纳米片的制备；
Se前驱体的制备：Se粉和十八烯加入玻璃瓶中；用聚四氟乙烯塞封口密封，超声后得到Se粉悬浊液体；
Cd前驱体的制备：氧化镉、油酸和十八烯加入三口烧瓶；磁力搅拌的条件下，通入氩气进行鼓泡除气，升温至240℃，直至溶液从浑浊变成无色透明，再降温至60℃；将透明前驱体溶液转移至玻璃取样瓶中，用聚四氟乙烯塞封口密封，通入氩气除气；
S前驱体的制备：辛硫醇和十八烯加入玻璃取样瓶；用聚四氟乙烯塞封口密封，通入氩气除气，摇晃使充分混合；
将氧化镉、十四酸、十八烯加入三口烧瓶；磁力搅拌的条件下，通入氩气进行鼓泡除气，在110℃温度下除气30min; 继续升温至285℃，直至溶液无色透明，再降温至90℃；注入Se前驱体溶液，再次除气；升温至195℃时，加入醋酸镉；继续升温至240℃，反应得到CdSe核纳米片；快速降至室温，当温度降至180℃时注入油酸；用正己烷-乙醇混合溶液离心提纯，最后将沉淀分散在正己烷中；
步骤2.2，CdSe/CdS核/壳纳米片的制备
取CdSe纳米片、Cd前驱体溶液和十八烯加入三口烧瓶；磁力搅拌的条件下，通入氩气鼓泡除气，室温除气40 min；升温至80℃继续除气20 min;在氩气保护下，设置300℃升温；温度升至180℃时，注入油胺；同时，硫前驱通过注射泵开始注入，速度为3 mL h-1；前驱体注入完成后，保持在300℃退火10 min；冷却至室温，在温度降至240℃时加入正己烷，降温至180℃时加入油酸；用甲醇进行原位提纯两次，去除溶液中过多的十八烯；加入正己烷-乙醇混合溶液离心提纯，将制备好的CdSe/CdS核/壳纳米片分散在正己烷中。
4.根据权利要求1所述一种基于量子限制斯塔克效应的光开关的制备方法，其特征在于，步骤2中在交叉电极之间沉积有序取向的II-VI族半导体纳米片NPLs层，具体为：
1)在聚四氟乙烯井内放置上交叉电极作为基板；
2)将油酸/二甘醇（OA / DEG）溶液加入井中，然后加入CdSe/CdS核/壳纳米片正己烷溶液；
3)用玻璃培养皿覆盖聚四氟乙烯井以减慢正己烷蒸发的速度；
4)己烷溶剂完全蒸发后，缓慢排出二甘醇DEG，使自组装膜沉积在基质上，纳米片面朝下，两侧边缘分别朝向正负电极。
5.根据权利要求1所述一种基于量子限制斯塔克效应的光开关的制备方法，其特征在于，电极间距为几个微米量级。
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