CN113299778B - 硒化铋/碲化铋超晶格红外双波段探测器及其制备方法 - Google Patents

硒化铋/碲化铋超晶格红外双波段探测器及其制备方法 Download PDF

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CN113299778B
CN113299778B CN202110579522.1A CN202110579522A CN113299778B CN 113299778 B CN113299778 B CN 113299778B CN 202110579522 A CN202110579522 A CN 202110579522A CN 113299778 B CN113299778 B CN 113299778B
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王东博
赵晨晨
王金忠
矫淑杰
曾值
刘雅欣
刘东昊
刘洋洋
张雨琦
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Harbin Institute of Technology
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Abstract

本发明公开了一种硒化铋/碲化铋超晶格红外双波段探测器及其制备方法，所述探测器包括蓝宝石衬底、Bi2Se3层、Bi2Te3层和金电极，蓝宝石衬底上生长Bi2Se3层，Bi2Se3层上生长Bi2Te3层，Bi2Se3与Bi2Te3之间形成Bi2Se3/Bi2Te3异质结，金电极设置在Bi2Se3层和Bi2Te3层上，制备步骤如下：一、在蓝宝石衬底上利用CVD技术生长Bi2Te3层；二、在生长的Bi2Se3层上利用CVD技术生长Bi2Te3层；三、利用磁控溅射技术在Bi2Se3层和Bi2Te3层表面沉积Au电极。本发明在蓝宝石衬底上利用CVD技术制备了Bi2Se3/Bi2Te3超晶格短波红外双波段超晶格，超晶格的红外发光峰分别在2.75μm和3.5μm，实现了红外双色探测材料结构。

Description

硒化铋/碲化铋超晶格红外双波段探测器及其制备方法
技术领域
本发明属于红外成像探测技术领域，涉及一种红外双波段探测器及其制备方法，具体涉及一种基于硒化铋（Bi2Se3）/碲化铋（Bi2Te3）超晶格红外双波段探测器及其制备方法。
背景技术
红外成像探测技术是图像监控家族中的重要成员，由红外探测成像的机理可知，任何温度高于绝对零度的物体都会由内部分子热运动不停向外界发射红外辐射，红外成像正是通过目标和背景的温差来成像。红外探测器把接收到的红外辐射转换成相应的电信号，是红外技术的核心。红外探测器按探测波长可分为短波红外（NIR， <3 μm）、中波红外（MIR，3 ~5 μm）、长波红外（LWIR，8 ~5 μm）和甚长波红外（VLWIR，14 ~30 μm）。其中短波红外具有良好的穿透性能，可以有效的应用在烟、雨、雾等复杂背景下成像探测。
能实现短波红外探测的材料主要包括HgCdTe （MCT）、红外量子阱（QWIP）和锑化物II型超晶格（InAs/Ga(In)Sb）等。
虽然经过多年的努力，基于碲镉汞（MCT）材料和III-V族量子阱材料的红外探测器和红外焦平面器件在长波红外波段的性能有了很大改善。但是，受材料本身和器件物理机制的限制，到目前为止，仍然存在一些难以克服的问题。
碲镉汞、量子阱、超晶格等材料均由分子束外延技术制备，制备工艺复杂，成本高。
此外，由于受限于晶格失配等问题，利用分子束外延技术制备红外短波双色探测材料，材料中会产生大量失配位错，失配位错是非辐射复合中心，会将光生载流子复合，影响了双色红外器件性能。
Bi2O2Se材料体系（Bi2O2Se、Bi2Se3、Bi2Te3、Sb2Te3等）作为新型拓扑绝缘体材料，在红外光探测方面具有优异的性能。首先，Bi2Se3/Bi2Te3超晶格结构由化学气相沉积技术（CVD）制备，与分子束外延技术相比，材料制备成本低。其次，Bi2Se3和Bi2Te3构成范德华异质结，不受失配位错影响，材料具有良好的晶体质量，因此可以制备高质量的红外双色探测材料。然后，Bi2O2Se材料体系其表面态由具有线性色散关系的狄拉克费米子组成，因而拥有着极高的载流子迁移率，会提高器件的灵敏度。
发明内容
为了解决受限于晶格失配等问题高质量红外双色探测材料制备工艺复杂、成本高，本发明提供了一种硒化铋/碲化铋超晶格红外双波段探测器及其制备方法。本发明采用CVD制备二维范德华异质结，避免了因为晶格失配造成的材料晶体质量下降的问题。
本发明的目的是通过以下技术方案实现的：
一种硒化铋/碲化铋超晶格红外双波段探测器，包括蓝宝石衬底、Bi2Se3层、Bi2Te3层和金电极，蓝宝石衬底上生长Bi2Se3层，Bi2Se3层上生长Bi2Te3层，Bi2Se3与Bi2Te3之间形成Bi2Se3/Bi2Te3异质结，金电极设置在Bi2Se3层和Bi2Te3层上。
本发明中，所述蓝宝石衬底的厚度2μm。
本发明中，所述Bi2Te3层和Bi2Se3层的厚度均为9~10个单原子层（3nm），探测器在2.75μm处短波红外的响应是固定的，但是中波红外区域的响应随Bi2Se3层和Bi2Te3层厚度的变化而变化。
本发明中，所述金电极分为顶电极和底电极，顶电极设置在Bi2Te3层上，底电极设置在Bi2Se3层上，顶电极和底电极连线垂直于Bi2Se3层和Bi2Te3层交界面，电极之间间距2mm，顶电极距交界面1mm，底电极距交界面1mm。
本发明中，所述金电极的厚度为50μm。
本发明，所述红外双波段探测器的工作原理如下：2.75μm处短波红外探测工作机理为利用Bi2Te3材料的光电导效应，Bi2Te3材料的带隙0.4eV左右，探测截止波长2.75μm，当入射光子能量大于Bi2Te3材料禁带宽度时，材料中电导率增加，实现2.75μm处短波红外响应；3.5μm处中波红外探测工作机理为利用9~10单原子层Bi2Te3材料和9~10单原子层Bi2Se3材料构成超晶格，利用超晶格形成微带，当入射光子能量大于等于超晶格间微带带隙，实现中波红外响应。
一种上述硒化铋/碲化铋超晶格红外双波段探测器的制备方法，包括如下步骤：
步骤一、在蓝宝石衬底上利用CVD技术生长Bi2Te3层，其中：Bi2Te3层的厚度为9~10单原子层，CVD工艺如下：（1）使用Bi2O3粉末作为Bi源，Se粒作Se源，100~300sccm氩气、10~30sccm氢气作为生长载气，生长设备使用双温区管式炉，将Bi2O3放置在高温区，升温至600~800℃；（2）将Se放置在低温区，升温至200~400℃；（3）采用化学气相沉积法在GaN衬底上生长Bi2Se3薄膜，控制生长时间为1~3小时；
步骤二、在生长的Bi2Se3层上利用CVD技术生长Bi2Te3层，Bi2Te3层的厚度为9~10单原子层，CVD工艺如下：（1）使用Bi2O3粉末作为Bi源，Te粒作Te源，100~300sccm氩气、10~30sccm氢气作为生长载气，生长设备使用双温区管式炉，将Bi2O3放置在高温区，升温至600~800℃；（2）将Te放置在低温区，升温至400~600℃；（3）用化学气相沉积法在Bi2Se3上生长Bi2Te3薄膜，控制生长时间为10~20分钟；
步骤三、利用磁控溅射技术在Bi2Se3层和Bi2Te3层表面沉积Au电极，控制磁控溅射的功率为30~50W，压强为0.5~1.0 Pa，氩气流量为20~40sccm，溅射时间为1~2 min。
相比于现有技术，本发明具有如下优点：
1、本发明在蓝宝石衬底上利用CVD技术制备了Bi2Se3/Bi2Te3超晶格短波红外双波段超晶格，超晶格的红外发光峰如图4所示，分别在2.75μm和3.5μm，实现了红外双色探测材料结构。
2、常用分子束外延制备的红外超晶格、碲镉汞、量子阱等红外材料制备成本高，工艺复杂，而CVD技术具有工艺简单，低成本的优点。
附图说明
图1为Bi2Se3的光致发光谱；
图2为Bi2Te3的光致发光谱；
图3为Bi2Te3/Bi2Se3异质结结构图；
图4为Bi2Te3/Bi2Se3异质结器件结构图；
图5为Bi2Te3/Bi2Se3异质结红外光致发光谱图。
具体实施方式
下面结合附图对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。
短波红外探测由于具有高穿透性可广泛应用于对地遥感探测、森林防火、高压电线路巡视等领域，本发明所设计的红外双色探测结构可应用于目前已有的短波红外探测预警相机，用于替换价格昂贵的碲镉汞、超晶格、量子阱的成像探测芯片材料。
如图4所示，所述红外双波段探测器包括蓝宝石衬底、Bi2Se3层、Bi2Te3层和金电极，蓝宝石衬底上生长9~10单原子层的Bi2Se3层，Bi2Se3层上生长9~10单原子层的Bi2Te3层，Bi2Se3与Bi2Te3之间形成Bi2Se3/Bi2Te3异质结，金电极分为顶电极和底电极，顶电极设置在Bi2Te3层上，底电极设置在Bi2Se3层上，顶电极和底电极连线垂直于Bi2Se3层和Bi2Te3层交界面，电极之间间距2mm，顶电极距交界面1mm，底电极距交界面1mm。具体制备方法如下：
步骤一、利用CVD技术在蓝宝石衬底上生长9~10单原子层的Bi2Se3层，生长工艺如下：使用0.1克99.995% Bi2O3粉末作为Bi源，使用1g 99.9999%纯度Se粒作Se源，使用200sccm氩气、15sccm氢气作为生长载气，生长设备使用双温区管式炉，Bi2O3放置在高温区升温至700℃，Se放置在低温区升温至300℃，蓝宝石放置在Bi2O3下方向5cm处，此处温度约为500℃，生长2小时，在蓝宝石上生长Bi2Se3薄膜。
CVD生长的Bi2Se3的光致发光谱如图1所示。由图1可以看出，样品在720~800 nm之间的发光峰与低维铋化物的间接带隙发光峰一致，表明所生长的为Bi2Se3材料。
步骤二、在Bi2Se3薄膜上利用CVD技术生长9~10单原子层的Bi2Te3层，生长工艺如下：使用0.1克99.995% Bi2O3粉末作为Bi源，使用1g 99.9999%纯度Te粒作Te源，使用200sccm氩气、15sccm氢气作为生长载气，生长设备使用双温区管式炉，Bi2O3放置在高温区升温至700℃，Te放置在低温区升温至500℃，Bi2Se3放置在Bi2O3下方向7cm处，此处温度约为450℃，生长15分钟，在Bi2Se3上生长Bi2Te3薄膜。
CVD生长的Bi2Te3光致发光谱如图2所示，生长异质结结构图如图3所示。由图2可以看出，样品在600~800 nm之间的发光峰与低维铋化物的间接带隙发光峰一致，表明所生长的为Bi2Te3材料。
步骤三、器件制备过程：利用磁控溅射技术（溅射功率40W，压强0.7 Pa，氩气流量30sccm，溅射时间1.5 min）在已制备的Bi2Se3/Bi2Te3异质结上蒸镀金电极，制备红外探测器。
异质结红外光致发光谱如图5所示，由图5可以看出，样品在2.75μm和3.5μm处有明显的光致发光峰。

Claims (9)

1.一种硒化铋/碲化铋超晶格红外双波段探测器，其特征在于所述探测器包括蓝宝石衬底、Bi2Se3层、Bi2Te3层和金电极，蓝宝石衬底上生长Bi2Se3层，Bi2Se3层上生长Bi2Te3层，Bi2Se3与Bi2Te3之间形成Bi2Se3/Bi2Te3异质结，金电极设置在Bi2Se3层和Bi2Te3层上，所述Bi2Te3层和Bi2Se3层的厚度均为9~10个单原子层，利用9~10单原子层Bi2Te3材料和9~10单原子层Bi2Se3材料构成超晶格，利用超晶格形成微带，当入射光子能量大于等于超晶格间微带带隙，实现中波红外响应。
2.根据权利要求1所述的硒化铋/碲化铋超晶格红外双波段探测器，其特征在于所述蓝宝石衬底的厚度2μm。
3.根据权利要求1所述的硒化铋/碲化铋超晶格红外双波段探测器，其特征在于所述金电极分为顶电极和底电极，顶电极设置在Bi2Te3层上，底电极设置在Bi2Se3层上。
4.根据权利要求3所述的硒化铋/碲化铋超晶格红外双波段探测器，其特征在于顶电极和底电极连线垂直于Bi2Se3层和Bi2Te3层交界面，电极之间间距2mm，顶电极距交界面1mm，底电极距交界面1mm。
5.根据权利要求1所述的硒化铋/碲化铋超晶格红外双波段探测器，其特征在于所述金电极的厚度为50μm。
6.一种权利要求1-5任一项所述硒化铋/碲化铋超晶格红外双波段探测器的制备方法，其特征在于所述方法包括如下步骤：
步骤一、在蓝宝石衬底上利用CVD技术生长Bi2Te3层；
步骤二、在生长的Bi2Se3层上利用CVD技术生长Bi2Te3层；
步骤三、利用磁控溅射技术在Bi2Se3层和Bi2Te3层表面沉积Au电极。
7.根据权利要求6所述的硒化铋/碲化铋超晶格红外双波段探测器的制备方法，其特征在于所述步骤一中，CVD工艺如下：（1）使用Bi2O3粉末作为Bi源，Se粒作Se源，100~300sccm氩气、10~30sccm氢气作为生长载气，生长设备使用双温区管式炉，将Bi2O3放置在高温区，升温至600~800℃；（2）将Se放置在低温区，升温至200~400℃；（3）采用化学气相沉积法在GaN衬底上生长Bi2Se3薄膜，控制生长时间为1~3小时。
8.根据权利要求6所述的硒化铋/碲化铋超晶格红外双波段探测器的制备方法，其特征在于所述步骤二中，CVD工艺如下：（1）使用Bi2O3粉末作为Bi源，Te粒作Te源，100~300sccm氩气、10~30sccm氢气作为生长载气，生长设备使用双温区管式炉，将Bi2O3放置在高温区，升温至600~800℃；（2）将Te放置在低温区，升温至400~600℃；（3）用化学气相沉积法在Bi2Se3上生长Bi2Te3薄膜，控制生长时间为10~20分钟。
9.根据权利要求6所述的硒化铋/碲化铋超晶格红外双波段探测器的制备方法，其特征在于所述步骤三中，磁控溅射的功率为30~50W，压强为0.5~1.0 Pa，氩气流量为20~40sccm，溅射时间为1~2 min。
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