CN113257944A - 一种异质结光电探测器及其制备方法 - Google Patents
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Abstract
本发明给出了一种使用不同类黑磷材料的不同双层堆垛结构来制备新型光电探测器的方法,该光电探测器包括衬底、下电极、双层GeS‑AB堆垛(GeS‑AB)、双层旋转SnS‑AD堆垛(tSnS‑AD)、上电极。本发明使用的双层GeS‑AB堆垛和双层旋转SnS‑AD堆垛能购成Ⅱ型半导体异质结,这里的GeS‑AB为受体材料,而tSnS‑AD为给体材料;且SnS材料和GeS材料在空气相对稳定,不容易和氧气发生反应;我们选用了特殊的电极材料,减小了接触电阻,有效的提升了器件的性能。
Description
技术领域
本发明涉及一种用不同类黑磷的不同堆垛结构实现半导体光电探测器的方法,属于半导体技术领域。
背景技术
近年以来,中国光电发展及其迅速,是继微电子产业发展之后又一大综合基础性的产业。预期2021年全球光电市场将达到7224亿美元。光电探测器是光电产业中重要的一环。光电探测器是许多设备的重要组成部分。比如在图像捕捉、光通信、激光雷达等应用中,都需要光电探测器快速将光信号转变为电学信号。目前使用较为广范的发展比较成熟的是硅光电探测器,其可以集成到CMOS技术在中,这不光降低了成本并扩大了应用的范围。但是,硅作为光吸收器件,其为间接带隙半导体,其间接带隙约为1.1eV,这限制硅光电探测器光响应范围仅在可见光和近红外光波段,并且限制了硅光电探测器的光吸收效率。人们一直在努力寻找更合适、更高效的新型半导体材料应用于激光器。
近几年来,新型半导体材料得到了长足的发展,出现了一系列的兴新二维半导体材料,如石墨烯、磷烯、MoS2等等,这些二维材料相比于传统的三维材料有着很多的优点,比如原子的厚度使得这些二维材料几乎是透明的,这使得这种二维材料可以集成到玻璃之中;又如二维材料具有良好的应变能力,可以应对很多特殊的环境。
本文中间关注了类黑磷烯材料,这些材料和磷烯类似,具有良好的光电性能,且相比于磷烯结构更加稳定。我们这里选用了2种类黑磷烯的稳定堆垛结构来制作半导体异质结,即双层旋转SnS-AD堆垛和双层GeS-AB堆垛。不同的堆垛结构有不同带隙和能级,将不同类型的堆垛组合起来可以形成不同的异质结结构,例如将双层旋转SnS-AD堆垛和GeS-AB堆垛组合起来可以形成Ⅱ型半导体异质结。这种半导体能带结构对于的电子有很好的收集作用,适合用来制作光电器件。
发明内容
1.技术问题:本发明的目的在于提供一种异质结半导体光电探测器及其制备方法,使用不同类黑磷烯的不同堆垛结构组成Ⅱ型异质结制备半导体光电探测器,提高光电探测器的效率。
2.技术方案:一种异质结半导体光电探测器,光电探测器包括衬底、下电极、双层旋转SnS-AD堆垛、双层GeS-AB堆垛、上电极,其中衬底为玻璃衬底,在玻璃衬底上层为堆叠的双层旋转SnS-AD堆垛,而双层旋转SnS-AD堆垛上堆叠着双层GeS-AB堆垛,下电极和玻璃衬底还有双层旋转SnS-AD堆垛相连接,上电极和双层GeS-AB堆垛相连接,上电极的面积大小为双层GeS-AB堆垛面积的25%。
所述的异质结半导体激光器中双层旋转SnS-AD堆垛厚度与为1nm-4nm,双层GeS-AB堆垛厚度为1nm-4nm,上电极金属电极,下电极为导电玻璃电极。
双层旋转SnS-AD堆垛和双层GeS-AB堆垛构成了一个Ⅱ型异质结;双层旋转SnS-AD堆和双层GeS-AB堆垛都为稳定的堆垛结构;双层旋转AD型SnS堆垛的第二层再相对于第一次层旋转了180°,然后第二层相当于相对第一层沿b方向移动了半个周期,而双层GeS-AB堆垛的结构的第二层相对于第一层沿着a方向移动了0.281个周期。
双层旋转SnS-AD堆垛和双层GeS-AB堆垛结构都是通过探针剥离的方法将初始结构错位得到的。
这里采用的下电极和衬底为一体化的导电玻璃。
一种所述的异质结光电探测器的制备方法,该制备方法包括如下步骤:
a.衬底和下电极的制备:光刻胶法制备衬底和下电极;
b.GeS薄膜的制备:采用化学浴生长法合成GeS薄膜,采用沉积法合成SnS薄膜;
c.SnS薄膜的制备:采用沉积法合成SnS薄膜;d.特殊类黑磷堆垛的制备:
1)将上述得到的GeS膜,在电子显微镜下,通过探针剥离的方法,剥离得到双层的GeS;
2)将1)得到的GeS在电子显微镜下,使用探针对其结构进行剥离,将第二层相对第一层翻转180°,然后让第二层相对于第一层移动0.281个周期,得到所要求的双层GeS-AB堆垛;
通过步骤1)和2)的方法得到双层旋转SnS-AD堆垛。
e.组合器件
将d得到的双层旋转SnS-AD堆垛通过二维材料转移装置转移到基底上,且使得双层旋转SnS-AD堆垛与ITO电极良好接触,然后将d得到的双层GeS-AB堆垛通过二维材料转移系统堆叠在双层旋转SnS-AD堆垛上方,对所得到的结构进行退火处理;
f.制作在上电极
在e得到的器件上表面蒸镀金属作为上电极,金属层均匀且纯度大于95wt%,上电极的面积大小为双层GeS-AB堆垛面积的25%。
衬底和下电极的制备具体是采用导电玻璃作为衬底和电极,首先在导电玻璃上涂上均匀的光刻胶,通过光刻技术得到对应电极图形的反图形,然后用刻蚀液腐蚀掉未被保护的部分,最后用丙酮溶液清洗掉多余的光刻胶,将得到的电极结构用酒精和去离子水进行超声清洗,然后用氮气吹干,使得下电极能够和玻璃衬底还有双层旋转SnS-AD堆垛相连接。
采用化学浴生长法合成GeS薄膜,具体步骤如下:将计量比的锗氯化二噁烷络合物、硫脲、油酰胺0LA分别在空气中轻微的磁力搅拌;将搅拌后的液体混合物超声处理,除去油胺中的空气;随后连接到Schlenk线,抽真空,除去水分和氧气;在磁力搅拌下通氮气进行惰性气体保护;将处理过后的液体混合物加热,随着温度的升高,液体逐渐变成了黄色透明溶液,反应混合物在氮气流中回流反应;反应结束将溶液冷却至室温,沉淀离心分离,洗涤真空干燥获得样品。
采用沉积法合成SnS薄膜,具体如下:先将去离子水通氮气,在水中加入药品,称取SnCl2-2H2O、Na2S2O3-5H2O、K4P2O7及添加剂C19H42BrN或CO(NH2)2,适量CuCl2-2H2O或AlCl3-6H2O溶于去离子水中,使用稀硫酸调节电乘积液pH值2.8~3.0,搅拌均匀备用,将三电极插入上述沉积液中,在恒温水浴进行沉积,搅拌速度恒定,恒电位沉积,沉积得到的薄膜放置在瓷舟中,再将瓷舟放置于管式炉中,退火,而后随炉冷却至室温。
有益效果:
1.本发明选用材料为二维材料,这类材料极致的厚度,可以使得生产的器件极薄。
2.本发明采用的ITO电极可以和半导体材料形成良好的欧姆接触,从而提升器件性能。
3.本发明选用的不同类黑磷材料具有近似的晶格结构和尺寸,容易达到晶格匹配,工艺简单。
4.本发明所采用的异质结为Ⅱ型异质结结构,所谓Ⅱ型异质结通常定义为该异质结的能带结构表现为:ΔEc(窄带与宽带导带底能量差)和ΔEv(窄带与宽带价带顶能量差)的符号相同;因此本结构就定义为双层旋转SnS-AD堆垛的CBM(导带底)在双层GeS-AB堆垛的CBM之上,而VBM(价带顶)也是双层旋转SnS-AD堆垛在双层GeS-AB堆垛VBM之上。Ⅱ型能带对准形成的内建电场能有效分离光生电子-空穴对,这对于光信号的收集和检测是有利的。
附图说明
图1为本发明提供的光电探测器的结构示意图。
图2为双层旋转tSnS-AD堆垛和双层旋转AB型GeS堆垛的能级分布图。
具体实施方式
本发明提供了一种基于不同类黑磷的不同堆垛的光电探测器,光电探测器包括衬底、下电极、双层旋转SnS-AD堆垛、双层GeS-AB堆垛、上电极,其中衬底为玻璃衬底,在其上层为堆叠的双层旋转SnS-AD堆垛,而双层旋转SnS-AD堆垛上堆叠着双层GeS-AB堆垛,下电极和衬底还有双层旋转SnS-AD堆垛相连接,上电极和双层GeS-AB堆垛相连接。
所述的异质结半导体光电探测器,所述的异质结半导体激光器中双层旋转SnS-AD堆垛厚度与为1nm-4nm,双层GeS-AB堆垛厚度为1nm-4nm。上电极金属电极,下电极为导电玻璃电极,可以选用铟锡氧化物玻璃(ITO)、铝锌氧化物玻璃(AZO)或铟锌氧化物玻璃(IZO)。可选地,上电极材料为业界常规选择,可以使用金属铝。。
所述的异质结光电探测器,双层旋转SnS-AD堆垛和双层GeS-AB堆垛构成了一个Ⅱ型异质结;双层旋转SnS-AD堆和双层GeS-AB堆垛都为稳定的堆垛结构;双层旋转AD型SnS堆垛的第二层再相对于第一次层旋转了180°,然后第二层相当于相对第一层沿b方向移动了半个周期,而双层GeS-AB堆垛的结构的第二层相对于第一层沿着a方向移动了0.281个周期。
所述的异质结光电探测器,双层旋转SnS-AD堆垛和双层GeS-AB堆垛结构都是通过探针剥离的方法将初始结构错位得到的。
所述的异质结光电探测器,其特征在于,这里采用的下电极和衬底为一体化的ITO玻璃,其能和双层旋转SnS-AD堆垛和下点击能形成良好的欧姆接触,从而显著提升器件性能。
所述的异质结光电探测器,所采用的异质结为Ⅱ型异质结结构,所谓Ⅱ型异质结通常定义为该异质结的能带结构表现为:ΔEc(窄带与宽带导带底能量差)和ΔEv(窄带与宽带价带顶能量差)的符号相同;因此本结构就定义为双层旋转SnS-AD堆垛的CBM(导带底)在双层GeS-AB堆垛的CBM之上,而VBM(价带顶)也是双层旋转SnS-AD堆垛在双层GeS-AB堆垛VBM之上。Ⅱ型能带对准形成的内建电场能有效分离光生电子-空穴对,这对于光信号的收集和检测是有利的。
本发明的异质结半导体光电探测器的制备方法包括以下步骤:
a.衬底和电极的制备
本发明中采用ITO导电玻璃作为衬底和电极,首先在ITO玻璃上涂上均匀的光刻胶,通过光刻技术得到对应电极图形的反图形,然后用ITO刻蚀液腐蚀掉未被保护的ITO,最后用丙酮溶液清洗掉多余的光刻胶,将得到的电极结构用酒精和去离子水进行超声清洗,然后用氮气吹干;最终使得下电极能够和玻璃衬底还有双层旋转SnS-AD堆垛相连接。
b.GeS薄膜的制备
本发明中采用化学浴生长法合成GeS薄膜,具体步骤如下:将0.2g锗氯化二噁烷络合物、0.4g硫脲、20ml油酰胺0LA分别加入到25ml的三颈瓶中,在空气中轻微的磁力搅拌;将搅拌后的液体混合物超声处理5min,除去油胺中的空气;随后将三颈瓶连接到Schlenk线,抽真空30min,除去水分和氧气;在磁力搅拌下通氮气30min进行惰性气体保护;将处理过后的液体混合物加热至593k,随着温度的升高,液体逐渐变成了黄色透明溶液。反应混合物在氮气流中593k温度下回流4h;反应结束将溶液冷却至室温,沉淀离心分离,用去离子水和无水乙醇洗涤多次,在40℃真空干燥4h获得样品。
c.SnS薄膜的制备
本发明采用沉积法合成SnS薄膜,具体如下:先将去离子水通氮气30min后,在水中加入药品,称取以定量的SnCl2-2H2O、Na2S2O3-5H2O、K4P2O7及添加剂C19H42BrN或CO(NH2)2,适量CuCl2-2H2O或AlCl3-6H2O溶于200ml去离子水中,使用稀硫酸调节电乘积液pH值2.8~3.0,搅拌均匀备用。将三电极插入上述乘积液中,在恒温水浴锅设定温度40℃~60℃条件下进行乘积,搅拌速度恒定300rpm/min,恒电位乘积实验,乘积时间位30min~50min。将1)沉积得到的薄膜放置在瓷舟中,再将瓷舟放置于管式炉中。设置退火程序,升温时间5℃/min,保温温度位350℃,保温时间为30min,调整保护气氩气通气速度为200ml/min~300ml/min。而后随炉冷却至室温。
d.特殊类黑磷堆垛的制备
1)将上述得到的GeS膜,在电子显微镜下,通过探针剥离的方法,剥离得到双层的GeS;
2)将1)得到的GeS在电子显微镜下,使用探针对其结构进行剥离,将第二层相对第一层翻转180°,然后让第二层相对于第一层移动0.281个周期,得到我们所要求的双层GeS-AB堆垛。
通过类似的方法得到双层旋转SnS-AD堆垛。
e.组合器件
将d得到的双层旋转SnS-AD堆垛通过二维材料转移装置转移到基底上,且使得双层旋转SnS-AD堆垛与ITO电极良好接触,然后将d得到的双层GeS-AB堆垛通过二维材料转移系统堆叠在双层旋转SnS-AD堆垛上方。对所得到的结构进行退火处理。
f.制作在上电极
在e得到的器件上表面蒸镀金属铝作为上电极,金属层均匀且纯度大于95wt%,上电极的面积大小为双层GeS-AB堆垛面积的25%左右。
实施例
a.衬底和电极的制备
本发明中采用ITO导电玻璃作为衬底和电极,首先在ITO玻璃上涂上均匀的光刻胶,通过光刻技术得到对应电极图形的反图形,然后用ITO刻蚀液腐蚀掉未被保护的ITO,最后用丙酮溶液清洗掉多余的光刻胶,将得到的电极结构用酒精和去离子水进行超声清洗,然后用氮气吹干。
b.GeS薄膜的制备
本发明中采用化学浴生长法合成GeS薄膜,具体步骤如下:将0.2g锗氯化二噁烷络合物、0.4g硫脲、20ml油酰胺0LA分别加入到25ml的三颈瓶中,在空气中轻微的磁力搅拌;将搅拌后的液体混合物超声处理5min,除去油胺中的空气;随后将三颈瓶连接到Schlenk线,抽真空30min,除去水分和氧气;在磁力搅拌下通氮气30min进行惰性气体保护;将处理过后的液体混合物加热至593k,随着温度的升高,液体逐渐变成了黄色透明溶液。反应混合物在氮气流中593k温度下回流4h;反应结束将溶液冷却至室温,沉淀离心分离,用去离子水和无水乙醇洗涤多次,在40℃真空干燥4h获得样品。
c.SnS薄膜的制备
本发明采用沉积法合成SnS薄膜,具体如下:先将去离子水通氮气30min后,在水中加入药品,称取以定量的SnCl2-2H2O、Na2S2O3-5H2O、K4P2O7及添加剂C19H42BrN或CO(NH2)2,适量CuCl2-2H2O或AlCl3-6H2O溶于200ml去离子水中,使用稀硫酸调节电乘积液pH值2.8~3.0,搅拌均匀备用。将三电极插入上述乘积液中,在恒温水浴锅设定温度40℃~60℃条件下进行乘积,搅拌速度恒定300rpm/min,恒电位乘积实验,乘积时间位30min~50min。将1)沉积得到的薄膜放置在瓷舟中,再将瓷舟放置于管式炉中。设置退火程序,升温时间5℃/min,保温温度位350℃,保温时间为30min,调整保护气氩气通气速度为200ml/min~300ml/min。而后随炉冷却至室温。
d.特殊类黑磷堆垛的制备
1)将上述得到的GeS膜,在电子显微镜下,通过探针剥离的方法,剥离得到双层的GeS;
2)将1)得到的GeS在电子显微镜下,使用探针对其结构进行剥离,将第二层相对第一层翻转180°,然后让第二层相对于第一层移动0.281个周期,得到我们所要求的双层GeS-AB堆垛。
通过类似的方法得到双层旋转SnS-AD堆垛。
e.组合器件
将d得到的双层旋转SnS-AD堆垛通过二维材料转移装置转移到基底上,且使得双层旋转SnS-AD堆垛与ITO电极良好接触,然后将d得到的双层GeS-AB堆垛通过二维材料转移系统堆叠在双层旋转SnS-AD堆垛上方。对所得到的结构进行退火处理。
f.制作在上电极
在e得到的器件上表面蒸镀金属铝作为上电极,金属层均匀且纯度大于95wt%,上电极的面积大小为双层GeS-AB堆垛面积的25%左右。
Claims (9)
1.一种异质结光电探测器,其特征在于:光电探测器包括衬底(1)、下电极(2)、双层旋转SnS-AD堆垛(3)、双层GeS-AB堆垛(4)、上电极(5),其中衬底为玻璃衬底,在玻璃衬底上层为堆叠的双层旋转SnS-AD堆垛(3),而双层旋转SnS-AD堆垛(3)上堆叠着双层GeS-AB堆垛(4),下电极(2)和玻璃衬底(1)还有双层旋转SnS-AD堆垛(3)相连接,上电极(5)和双层GeS-AB堆垛(4)相连接,上电极的面积大小为双层GeS-AB堆垛面积的25%。
2.根据权利要求1所述的异质结光电探测器,其特征在于,所述的异质结半导体激光器中双层旋转SnS-AD堆垛厚度与为1nm-4nm,双层GeS-AB堆垛厚度为1nm-4nm,上电极金属电极,下电极为导电玻璃电极。
3.根据权利要求1所述的异质结光电探测器,其特征在于,双层旋转SnS-AD堆垛(3)和双层GeS-AB堆垛(4)构成了一个Ⅱ型异质结;双层旋转SnS-AD堆和双层GeS-AB堆垛都为稳定的堆垛结构;双层旋转AD型SnS堆垛的第二层再相对于第一次层旋转了180°,然后第二层相当于相对第一层沿b方向移动了半个周期,而双层GeS-AB堆垛的结构的第二层相对于第一层沿着a方向移动了0.281个周期。
4.根据权利要求1所述的异质结光电探测器,其特征在于,双层旋转SnS-AD堆垛(3)和双层GeS-AB堆垛(4)结构都是通过探针剥离的方法将初始结构错位得到的。
5.根据权利要求1所述的异质结光电探测器,其特征在于,这里采用的下电极(2)和衬底(1)为一体化的导电玻璃。
6.一种权利要求1~5任一所述的异质结光电探测器的制备方法,其特征在于,该制备方法包括如下步骤:
a.衬底和下电极的制备:光刻胶法制备衬底和下电极;
b.GeS薄膜的制备:采用化学浴生长法合成GeS薄膜,采用沉积法合成SnS薄膜;
c.SnS薄膜的制备:采用沉积法合成SnS薄膜;d.特殊类黑磷堆垛的制备:
1)将上述得到的GeS膜,在电子显微镜下,通过探针剥离的方法,剥离得到双层的GeS;
2)将1)得到的GeS在电子显微镜下,使用探针对其结构进行剥离,将第二层相对第一层翻转180°,然后让第二层相对于第一层移动0.281个周期,得到所要求的双层GeS-AB堆垛;
通过步骤1)和2)的方法得到双层旋转SnS-AD堆垛。
e.组合器件
将d得到的双层旋转SnS-AD堆垛通过二维材料转移装置转移到基底上,且使得双层旋转SnS-AD堆垛与导电玻璃电极良好接触,然后将d得到的双层GeS-AB堆垛通过二维材料转移系统堆叠在双层旋转SnS-AD堆垛上方,对所得到的结构进行退火处理;
f.制作在上电极
在e得到的器件上表面蒸镀金属作为上电极,金属层均匀且纯度大于95wt%,上电极的面积大小为双层GeS-AB堆垛面积的25%。
7.如权利要求6所述的异质结光电探测器的制备方法,其特征在于,衬底和下电极的制备具体是采用导电玻璃作为衬底和电极,首先在导电玻璃上涂上均匀的光刻胶,通过光刻技术得到对应电极图形的反图形,然后用刻蚀液腐蚀掉未被保护的部分,最后用丙酮溶液清洗掉多余的光刻胶,将得到的电极结构用酒精和去离子水进行超声清洗,然后用氮气吹干,使得下电极(2)能够和玻璃衬底(1)还有双层旋转SnS-AD堆垛(3)相连接。
8.如权利要求6所述的异质结光电探测器的制备方法,其特征在于,采用化学浴生长法合成GeS薄膜,具体步骤如下:将计量比的锗氯化二噁烷络合物、硫脲、油酰胺0LA分别在空气中轻微的磁力搅拌;将搅拌后的液体混合物超声处理,除去油胺中的空气;随后连接到Schlenk线,抽真空,除去水分和氧气;在磁力搅拌下通氮气进行惰性气体保护;将处理过后的液体混合物加热,随着温度的升高,液体逐渐变成了黄色透明溶液,反应混合物在氮气流中回流反应;反应结束将溶液冷却至室温,沉淀离心分离,洗涤真空干燥获得样品。
9.如权利要求6所述的异质结光电探测器的制备方法,其特征在于,采用沉积法合成SnS薄膜,具体如下:先将去离子水通氮气,在水中加入药品,称取SnCl2-2H2O、Na2S2O3-5H2O、K4P2O7及添加剂C19H42BrN或CO(NH2)2,适量CuCl2-2H2O或AlCl3-6H2O溶于去离子水中,使用稀硫酸调节电乘积液pH值2.8~3.0,搅拌均匀备用,将三电极插入上述沉积液中,在恒温水浴进行沉积,搅拌速度恒定,恒电位沉积,沉积得到的薄膜放置在瓷舟中,再将瓷舟放置于管式炉中,退火,而后随炉冷却至室温。
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