CN113013279B - 碲镉汞-黑磷范德华异质结红外偏振探测器及制备方法 - Google Patents

碲镉汞-黑磷范德华异质结红外偏振探测器及制备方法 Download PDF

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CN113013279B
CN113013279B CN202110107189.4A CN202110107189A CN113013279B CN 113013279 B CN113013279 B CN 113013279B CN 202110107189 A CN202110107189 A CN 202110107189A CN 113013279 B CN113013279 B CN 113013279B
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焦韩雪
陈艳
王建禄
孟祥建
沈宏
林铁
褚君浩
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Shanghai Institute of Technical Physics of CAS
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Abstract

本发明公开了一种碲镉汞‑黑磷范德华异质结红外偏振探测器及制备方法。探测器的结构自下而上依次为衬底、碲镉汞材料、绝缘层、二维半导体黑磷、金属电极。首先在衬底上生长碲镉汞材料，通过紫外光刻和氩离子刻蚀去除部分碲镉汞，采用电子束蒸发的方法填充氧化铝作为绝缘层，利用聚碳酸亚丙酯薄膜辅助定点转移二维半导体材料黑磷在碲镉汞和绝缘层的交界处，通过电子束光刻技术结合剥离工艺制备金属源漏电极，形成碲镉汞范德华异质结红外偏振探测器结构。该器件结构可在无外加偏置电压的条件下实现中波红外波段的探测功能，有效降低了器件功耗；且可在无附加光结构的条件下实现偏振探测功能，大大简化了偏振探测器的器件结构。

Description

碲镉汞-黑磷范德华异质结红外偏振探测器及制备方法
技术领域
本发明涉及红外探测技术领域，特别涉及到一种红外偏振光电探测器件，具体指一种基于光伏响应机制的碲镉汞-黑磷范德华异质结器件及制备方法。
背景技术
红外探测器能将所接收到的红外辐射转换成其他物理量，如电压、电流等，以便于探测并计量红外辐射能量。红外探测器在军事、医学、生物学、天文学等许多领域都具有重要而广泛的应用。窄带隙半导体具有高光学吸收系数、高电子迁移率、低产热速率等基本特点，特别适合用于制备高性能的红外探测器。其中碲镉汞材料体系具有可调节的带隙宽度，实现了高性能的红外响应，响应范围可覆盖近红外至远红外，因而成为目前红外探测应用领域主流材料体系。目前，高性能红外探测***已经发展到了第三代。其特点为高性能、高分辨率、多色探测功能，且在高温非制冷条件下具有更强的工作能力，同时要求器件成本与制冷成本继续降低。因此，基于半导体异质结的光伏型探测器结构在新一代红外探测***中仍然具有突出的优势。
目前，基于碲镉汞体系的平面结、台面结、环孔结构等器件均有制备与应用。常用的器件制备方法有离子注入形成结区以及异质外延生长中进行原位掺杂后进行台面刻蚀。由于碲镉汞中汞-碲键合较弱，离子注入与台面刻蚀过程中往往会引入大量晶格损伤，带来反型问题，为理想结区的形成带来困难。随着探测器尺寸的缩小，材料缺陷对器件性能的影响更加突出，引起性能下降、器件漏电等多种问题。而现阶段国内在制备高质量、大面积碲镉汞材料方面仍存在一定困难，因此设法尽量减少器件制备中引起的材料损伤是降低对器件性能影响的重要手段。
范德华异质集成是指利用分子间作用力形成的异质集成，是一种新兴的构建半导体异质结结构的手段，与传统异质结的最大区别在于其界面间不存在化学键作用，可达到原子级的平整界面，避免了传统异质结制备过程中存在的晶格失配、热失配、应力失配等问题，在构建无损伤异质界面方面具有极大吸引力，有助于展现材料的本征性能。而低维半导体材料由于层间依靠范德华力结合，无悬挂键，在范德华集成方面具有天然的优势。且多种二维材料，如黑磷、硒化锗等，具有结构各向异性的特点，能够对不同方向的偏振光产生不同强度的响应，因此可用于实现偏振探测功能。
为了解决传统光电探测器制备工艺复杂、界面损伤等问题，实现高性能、多功能的新一代红外探测器件，本发明针对红外光电探测技术，提出了一种基于碲镉汞范德华异质结的新型红外探测器结构。通过范德华异质集成，将碲镉汞材料与低维半导体材料黑磷的优异性能相结合，获得了能够在无偏置电压的条件下工作的中波红外偏振探测器件，该器件避免了传统偏振探测器中复杂的光学结构，能够实现多维度信息获取，具有功耗低、响应迅速、结构简单等优点。
发明内容
本发明提出了一种碲镉汞范德华异质结红外偏振探测器及制备方法，该器件能够实现红外偏振探测功能，为高性能、低功耗、多功能的新一代红外探测器件的研制开辟了道路。
上述发明将传统红外光电材料碲镉汞与新兴二维材料黑磷相结合形成范德华异质结，将两种不同半导体材料的特点与优势相结合，利用二者的红外吸收特性实现了中波红外探测功能；并且利用二维半导体材料黑磷结构的各向异性，实现了中红外波段的偏振探测功能。该器件基于光伏响应机制工作，能够在无外加偏置电压的情况下实现的红外偏振探测功能，具有功耗低、灵敏度高、响应迅速等优点。
本发明指一种碲镉汞范德华异质结红外偏振探测器及制备方法，其特征在于，器件结构自下而上为：
-衬底1，
-碲镉汞材料2、
-部分覆盖碲镉汞材料2的绝缘层3、
-覆盖在碲镉汞材料2和绝缘层3上二维半导体材料4、
-接触碲镉汞材料2的碲镉汞侧金属电极5、
-接触绝缘层3和二维半导体材料4的二维材料侧金属电极6、
其中衬底1为本征锗衬底，厚度0.9毫米；
其中碲镉汞材料2的截止波长为4.3微米，厚度8微米；
其中绝缘层材料3为氧化铝，厚度100到150纳米；
其中二维半导体材料4为黑磷，厚度50到150纳米；
其中碲镉汞侧金属电极5、二维材料侧金属电极6为钛/金电极，钛厚度为10到15纳米，金厚度为35到45纳米。
本发明指一种碲镉汞范德华异质结红外偏振探测器及制备方法，其特征在于器件制备包括以下步骤：
1)碲镉汞材料生长
在本征锗衬底上通过分子束外延方法制备碲镉汞材料，厚度为8微米。
2)绝缘层制备
在碲镉汞材料上通过紫外光刻形成掩膜，露出部分碲镉汞材料，通过氩离子刻蚀去除100到150纳米厚度的碲镉汞，通过电子束蒸发的方法填充100到150纳米厚的氧化铝，利用丙酮浸泡去除光刻掩膜。
3)二维半导体材料制备及转移
采用机械剥离方法得到厚度在50到150纳米的二维半导体材料黑磷，将其转移在硅衬底上。在该二维半导体上覆盖一层聚碳酸亚丙酯薄膜，加热使其与该二维半导体充分接触，降温后在衬底上取下该聚碳酸亚丙酯薄膜，此时二维半导体被聚碳酸亚丙酯吸附，在显微镜下移动薄膜，使得二维半导体与碲镉汞和氧化铝交界处对准，加热使其缓慢接触，降温后将样品置于丙酮中浸泡，使聚碳酸亚丙酯完全溶解，至此制备好碲镉汞-黑磷范德华异质结。
4)金属电极的制备
采用电子束曝光技术，结合电子束蒸发金属及剥离工艺制备碲镉汞侧金属电极5和二维材料侧金属电极6，电极为钛/金，钛厚度为10到15纳米，金厚度为35到45纳米。
本发明有以下优点：(1)通过将传统红外光电材料碲镉汞与新兴二维材料黑磷相结合形成范德华异质结，器件基于光伏响应机制工作，能够在无外加偏置电压的条件下实现中波红外探测功能，器件具有功耗低、灵敏度高、响应速度快等优点；(2)利用二维半导体材料黑磷结构的各向异性，在无附加光学结构的情况下实现中红外波段的偏振探测功能，避免了传统偏振探测器复杂的光学结构，具有结构简单、容易制备等优点；(3)由于二维材料具有无悬挂键的原子级平整表面，且在器件制备过程异质结界面依靠范德华力结合，因此对异质结界面无损伤，能够得到近完美的异质结界面，避免了传统离子注入工艺中对界面的破坏。
附图说明
图1为碲镉汞范德华异质结红外偏振探测器结构截面示意图。图中：1衬底，2碲镉汞材料、3绝缘层、4二维半导体材料、5金属电极、6金属电极。
图2为碲镉汞范德华异质结红外偏振探测器光电响应特性图；其中：图2(a)为一种碲镉汞范德华异质结红外偏振探测器在偏置电压为零的情况下对4324nm波长中波红外激光的光电响应特性；图2(b)为为一种碲镉汞范德华异质结红外偏振探测器在偏置电压为零的情况下对4135nm波长中波红外激光的光电响应特性；图2(c)为一种碲镉汞范德华异质结红外偏振探测器在偏置电压为零的情况下对4034nm波长中波红外激光的光电响应特性。
图3为一种碲镉汞范德华异质结红外偏振探测器在波长为4034纳米激光照射下产生的光电流与入射光偏振角的关系。
具体实施方式
实施例1：
下面结合附图对本发明的实施例1作详细说明：
本发明研制了黑磷-碲镉汞混合维度异质结红外探测器。通过将传统红外光电材料碲镉汞与新兴二维材料黑磷相结合形成范德华异质结，利用黑磷的偏振吸收特性与二者的红外吸收特性，将二者的特点与优势相结合，得到了具有偏振探测功能的红外光电探测器。
具体步骤如下：
1.衬底选择
选用厚度0.9毫米的本征锗做为衬底。
2.碲镉汞材料制备
通过分子束外延方法在锗衬底表面制备8微米厚度碲镉汞材料。
3.绝缘层制备
在碲镉汞材料上通过光刻形成掩膜，通过氩离子刻蚀去除150纳米厚度的碲镉汞，通过电子束蒸发的方法蒸镀150纳米厚的氧化铝。
4.二维半导体材料制备及转移
采用机械剥离方法得到厚度100纳米的二维半导体材料黑磷，将其转移在硅衬底上。在该二维半导体上覆盖一层聚碳酸亚丙酯薄膜，加热使其与该二维半导体充分接触，降温后在衬底上取下该聚碳酸亚丙酯薄膜，此时二维半导体被聚碳酸亚丙酯吸附，在显微镜下移动薄膜，使得二维半导体与碲镉汞和氧化铝交界处对准，加热使其缓慢接触，降温后将样品置于丙酮中浸泡，使聚碳酸亚丙酯完全溶解，至此制备好碲镉汞-黑磷范德华异质结。
5.金属电极制备
利用电子束光刻方法制备金属电极图形；利用电子束蒸发技术制备金属电极，钛15纳米，金45纳米；结合剥离方法，剥离金属膜，获得金属电极。器件的最终结构如图1所示。
6.红外光电性能测试
在器件偏置电压为零的情况下，用波长为4324纳米的中波红外激光光源照射器件，测试器件的电流随时间的变化，实验结果如图2(a)所示。可以看到在偏置电压为零的情况下，随着激光的开启与关闭，器件电流发生迅速且明显的变化，该器件对波长4324纳米的激光表现出灵敏的光响应，表明所研制的黑磷-碲镉汞异质结器件能够实现中波红外探测功能，且器件可工作在零偏置条件下，无需外加电压，从而有效降低了探测器功耗。
实例2：
下面结合附图对本发明的实例2作详细说明：
本发明研制了黑磷-碲镉汞混合维度异质结红外探测器。通过将传统红外光电材料碲镉汞与新兴二维材料黑磷相结合形成范德华异质结，利用黑磷的偏振吸收特性与二者的红外吸收特性，将二者的特点与优势相结合，得到了具有偏振探测功能的红外光电探测器。
具体步骤如下：
1.衬底选择
选用厚度0.9毫米的本征锗做为衬底。
2.碲镉汞材料制备
通过分子束外延方法在锗衬底表面制备8微米厚度碲镉汞材料。
3.绝缘层制备
在碲镉汞材料上通过光刻形成掩膜，通过氩离子刻蚀去除120纳米厚度的碲镉汞，通过电子束蒸发的方法蒸镀120纳米厚的氧化铝。
4.二维半导体材料制备及转移
采用机械剥离方法得到厚度50纳米的二维半导体材料黑磷，将其转移在硅衬底上。在该二维半导体上覆盖一层聚碳酸亚丙酯薄膜，加热使其与该二维半导体充分接触，降温后在衬底上取下该聚碳酸亚丙酯薄膜，此时二维半导体被聚碳酸亚丙酯吸附，在显微镜下移动薄膜，使得二维半导体与碲镉汞和氧化铝交界处对准，加热使其缓慢接触，降温后将样品置于丙酮中浸泡，使聚碳酸亚丙酯完全溶解，至此制备好碲镉汞-黑磷范德华异质结。
5.金属电极制备
利用电子束光刻方法制备金属电极图形；利用电子束蒸发技术制备金属电极，钛10纳米，金35纳米；结合剥离方法，剥离金属膜，获得金属电极。器件的最终结构如图1所示。
6.红外光电性能测试
在器件偏置电压为零的情况下，用波长为4135纳米的中波红外激光光源照射器件，测试器件的电流随时间的变化，实验结果如图2(b)所示。可以看到在偏置电压为零的情况下，随着激光的开启与关闭，器件电流发生迅速且明显的变化，该器件对波长4135纳米的激光表现出灵敏的光响应，表明所研制的黑磷-碲镉汞异质结器件能够实现中波红外探测功能，且器件可工作在零偏置条件下，无需外加电压，从而有效降低了探测器功耗。
实例3：
下面结合附图对本发明的实例3作详细说明：
本发明研制了黑磷-碲镉汞混合维度异质结红外探测器。通过将传统红外光电材料碲镉汞与新兴二维材料黑磷相结合形成范德华异质结，利用黑磷的偏振吸收特性与二者的红外吸收特性，将二者的特点与优势相结合，得到了具有偏振探测功能的红外光电探测器。
具体步骤如下：
1.衬底选择
选用厚度0.9毫米的本征锗做为衬底。
2.碲镉汞材料制备
通过分子束外延方法在锗衬底表面制备8微米厚度碲镉汞材料。
3.绝缘层制备
在碲镉汞材料上通过光刻形成掩膜，通过氩离子刻蚀去除100纳米厚度的碲镉汞，通过电子束蒸发的方法蒸镀100纳米厚的氧化铝。
4.二维半导体材料制备及转移
采用机械剥离方法得到厚度150纳米的二维半导体材料黑磷，将其转移在硅衬底上。在该二维半导体上覆盖一层聚碳酸亚丙酯薄膜，加热使其与该二维半导体充分接触，降温后在衬底上取下该聚碳酸亚丙酯薄膜，此时二维半导体被聚碳酸亚丙酯吸附，在显微镜下移动薄膜，使得二维半导体与碲镉汞和氧化铝交界处对准，加热使其缓慢接触，降温后将样品置于丙酮中浸泡，使聚碳酸亚丙酯完全溶解，至此制备好碲镉汞-黑磷范德华异质结。
5.金属电极制备
利用电子束光刻方法制备金属电极图形；利用电子束蒸发技术制备金属电极，钛12纳米，金40纳米；结合剥离方法，剥离金属膜，获得金属电极。器件的最终结构如图1所示。
6.红外光电性能测试
在器件偏置电压为零的情况下，用频率为1赫兹、波长为4034纳米的中波红外激光光源照射器件，测试器件的电流随时间的变化，实验结果如图2(c)所示。可以看到在偏置电压为零的情况下，随着激光的开启与关闭，器件电流发生迅速且明显的变化，该器件对波长4034纳米的激光表现出灵敏的光响应，表明所研制的黑磷-碲镉汞异质结器件能够实现中波红外探测功能，且器件可工作在零偏置条件下，无需外加电压，从而有效降低了探测器功耗。
在器件偏置电压为零的情况下，用波长为4034纳米的中波红外激光光源照射器件，在所使用的中波红外激光器前加偏振片，使激光变成线偏振光，通过可旋转的半波片改变线偏振光偏转的角度。如图3所示，当偏振光角度发生变化时，器件的光电流大小也随之发生改变，表明所研制的碲镉汞-黑磷异质结器件在中波红外波段具有偏振灵敏性。该器件能够在无需外加偏置电压和光学结构的情况下实现红外偏振探测功能，简化了偏振探测器结构，使红外偏振探测器件的制备难度大大降低。
以上所述仅为本发明的优选实施例，不用于限制本发明，对于本领域内的一般技术人员，本发明可以有各种更改和变化。凡在本发明的思想和原则之内，所作的任何修改、替换、改进等，均包含在本发明的保护范围内。

Claims (2)

1.一种碲镉汞-黑磷范德华异质结红外偏振探测器，其特征在于，器件结构自下而上为：
衬底(1)、碲镉汞材料(2)、绝缘层(3)、覆盖在碲镉汞材料(2)和绝缘层(3)上的二维半导体材料(4)、接触碲镉汞材料(2)的碲镉汞侧金属电极(5)、接触绝缘层(3)和二维半导体材料(4)的二维材料侧金属电极(6)，所述的绝缘层(3)覆盖在碲镉汞材料(2)上被去除部分位置处，且其厚度与被去除的碲镉汞厚度相同；其中：
所述的衬底(1)为本征锗衬底，厚度0.9毫米；
所述的碲镉汞材料(2)为截止波长4.3微米的碲镉汞，厚度8微米；
所述的绝缘层(3)为氧化铝，厚度100到150纳米；
所述的二维半导体材料(4)为黑磷，厚度50到150纳米；
所述的碲镉汞侧金属电极(5)和二维材料侧金属电极(6)为钛和金双层电极，下层钛厚度为10到15纳米，上层金厚度为35到45纳米。
2.一种制备如权利要求1所述碲镉汞-黑磷范德华异质结红外偏振探测器的方法，其特征在于器件制备包括以下步骤：
1)在衬底(1)上通过分子束外延方法制备碲镉汞材料(2)；
2)在碲镉汞材料(2)上通过紫外光刻形成掩膜，通过氩离子刻蚀去除一定厚度的碲镉汞，通过电子束蒸发的方法填充绝缘层(3)，利用丙酮浸泡去除光刻掩膜；
3)采用机械剥离方法得到二维半导体材料(4)，将其转移在硅衬底上，在该二维半导体材料上覆盖一层聚碳酸亚丙酯薄膜，加热使其与该二维半导体材料充分接触，降温后在硅衬底上取下该聚碳酸亚丙酯薄膜，此时二维半导体材料被聚碳酸亚丙酯吸附，在显微镜下移动薄膜，使得二维半导体材料与碲镉汞和氧化铝交界处对准，加热使其缓慢接触，降温后将样品置于丙酮中浸泡，使聚碳酸亚丙酯完全溶解，至此制备好碲镉汞-黑磷范德华异质结；
4)金属电极的制备：采用电子束曝光技术，结合电子束蒸发金属及剥离工艺制备碲镉汞侧金属电极(5)和二维材料侧金属电极(6)，电极材料采用钛和金，钛厚度为10到15纳米，金厚度为35到45纳米，完成碲镉汞-黑磷范德华异质结红外偏振探测器的制备。
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