CN113299777A - 一种铅盐红外探测器芯片结构及其制备方法 - Google Patents
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Abstract
本发明涉及红外探测器芯片,特指一种铅盐红外探测器芯片结构及其制备方法。所述铅盐红外探测器芯片结构从下至上包括图形化衬底、铅盐化合物薄膜、钝化层和金属电极层;采用衬底预处理方式获得图形化衬底,然后在图形化衬底上通过化学沉积或者物理沉积等方法沉积铅盐薄膜;在图形化衬底上获得的铅盐薄膜表面会继承衬底上图形,从而获得表面粗化的铅盐薄膜。整个制备工艺简单、易控,制备装置简单、成本低廉,适用于批量化生产制造。
Description
技术领域
本发明涉及红外探测器芯片,特指一种铅盐红外探测器芯片结构及其制备方法,具体涉及了一种铅盐芯片表面粗化及制作方法。
背景技术
以PbS、PbSe、PbTe等为代表的铅盐化合物是一种重要半导体材料。与其它半导体材料相比,铅盐化合物半导体具有独特的性质,如具有小的直接带隙能,较大的激子玻尔半径及较大的非线性光学系数等,这些性质使得铅盐在近红外区域有较强的响应,得到了广泛的关注。在非线性光学装置、红外光学探测器、柔性太阳能电池和显示等方面得到广泛应用。以铅盐化合物半导体材料制成的薄膜型本征红外光导探测器由于性能优良、结构牢靠,且制造工艺简便,能做成单元、多元与镶嵌阵列,探测率高被广泛用于军事和民用工业中,具有不可替代的作用。
近年来,针对高质量、高性能铅盐薄膜的需求,各种新颖的制备方法及措施屡见报道,如化学浴沉积法(CBD)、电化学沉积法(ECD)、溶胶-凝胶法(SGM)等。其中CBD法相比其它方法而言,具有设备简单、成本低、易操控,能够制备大面积质量均匀的薄膜,成膜结晶良好且为(200)择优取向的立方结构等优点备受研究者的青睐。铅盐红外探测器工作原理是接收光能并将其转化为电能,通过在基底(例如玻璃、陶瓷及硅等)上沉积铅盐薄膜(PbS、PbSe、PbTe等)来制备铅盐光导探测器。由于铅盐化合物折射率较大(PbS折射率3.9),而空气折射率为1,两者之间折射率相差较大,所以铅盐化合物薄膜与空间界面上存在较严重的全反射现象,导致入射的光线仅有少部分可以被铅盐薄膜吸收,严重限制铅盐红外探测器的灵敏度。
铅盐红外探测器的灵敏度特性与铅盐薄膜表面微结构密切相关,而铅盐红外探测器芯片的制备工艺直接影响薄膜表面微结构。国内外关于铅盐薄膜制备方法的报道中,极少涉及到制备工艺对薄膜表面微结构和红外探测器灵敏度的影响。如E.M.Larramendi等人(Larramendi E M,Calzadilla O,A González-Arias,et al.Thin Solid Films,2001,389(1-2):301-306.)用CBD法在玻璃基片上制备PbS薄膜,研究了溶液中Br-1离子对薄膜表面形貌及器件光敏性的影响;J.Puiso等人(Puiso J,Tamulevicius S,Laukaitis G.ThinSolid Films,2002,403:457-461.)用连续离子层吸附反应(SILAR)在Si基片上制备PbS薄膜,对薄膜的晶型、晶粒尺寸、微结构、粗糙度与原子组成进行了详细研究。国内司俊杰等人(司俊杰,万海林,陈湘伟,陈凤金,黄战利,张庆军,孙维国.红外技术,2007(03):143-146.)通过优化沉淀方法、敏化过程,改善了PbS薄膜成分、形貌的均匀性和探测器的光电响应度。从上面分析可知,影响薄膜材料性能的因素有很多,其中样品的微观结构和表面形貌特征对薄膜的吸收特性和电学性质的影响是不容忽视的。因此,有必要寻求一种铅盐红外探测器芯片的表面粗化结构或工艺,该结构或工艺要求能有效减少或降低全反射现象,进而提高探测器响应灵敏度,同时制备过程可控且制备工艺简单可进一步降低制造成本。
发明内容
有鉴于此,本发明的目的在于提供铅盐红外探测器芯片结构及其制备方法,所制备出的铅盐红外探测器芯片表面具有纳米级微尺寸结构,得到的纳米级微尺寸粗化表面可有效减少或避免全反射现象,具有较好的均匀性和光敏特性。整个制备工艺简单、易控,制备装置简单、成本低廉,适用于批量化生产制造。
本发明所述的纳米级微尺寸粗化表面是指采用衬底预处理方式获得图形化衬底,然后在图形化衬底上通过化学沉积或者物理沉积等方法沉积铅盐薄膜;在图形化衬底上获得的铅盐薄膜表面会继承衬底上图形,从而获得表面粗化的铅盐薄膜。
本发明提出一种铅盐红外探测器芯片结构,其特征如图5所示,从下至上包括图形化衬底、铅盐化合物薄膜、钝化层和金属电极层;
进一步的,所述图形化衬底获得方式包括湿法腐蚀、干法刻蚀、机械摩擦或其它可以达到同样纳米级微尺寸的方法中的任一项;所述的铅盐化合物薄膜包括PbS、PbSe、PbTe或对红外光有响应的其它铅盐化合物中的一种。
作为本发明的另一方面,提出了一种铅盐红外探测器制备方法,参照图1-图5所示,铅盐红外探测器制备流程如图6所示,包括如下步骤:
1)衬底预处理:将衬底放入丙酮溶液中超声清洗,然后放入无水乙醇溶液超声清洗,接着用去离子水超声清洗,最后用氮气吹干得到如图1所示的原始衬底;
2)将步骤1中获得的衬底进行图形化处理,在衬底表面指定位置加工出纳米级微尺寸形貌,形成如图2所示的图形化衬底;
3)将步骤2中获得的图形化衬底上沉积铅盐化合物薄膜,如图3所示,此时薄膜的形貌将会继承步骤2中的加工出来的形貌;
4)如图4所示,在沉积好的铅盐化合物薄膜表面生长一层保护铅盐化合物薄膜的钝化层;
5)如图5所示,采用光刻剥离工艺在铅盐化合物薄膜上制备金属电极层,完成芯片制备。
进一步的,所述衬底材料选自玻璃、陶瓷、硅和蓝宝石中的任意一种。
进一步的,所述图形化衬底是指在衬底指定部分(沉积铅盐薄膜部分)制备纳米级微尺寸图形,剩余部分(制备金属电极部分)不做处理,其中沉积铅盐薄膜部分图形的排列可以是规则有序分布的图形,也可以是不规则无序分布的图形,或者是可以达到增加光吸收,减少全反射的任意形状。
进一步的,所述的铅盐薄膜沉积方式包括化学浴沉积、化学气相沉积、物理气相沉积、原子层沉积、连续离子层吸附、电化学沉积、溶胶-凝胶法中可以进行宏观和微观均匀沉积的方法中的任一项。
进一步的,所述的钝化层材料为As2S3、CdTe、ZnSe、Al2O3、MgF2和SiO2中的任一种。
进一步的,步骤5所述的金属电极层制备方式为电子束蒸发或磁控溅射方式。
进一步的,所述的金属电极层包括金、银、铝、铬、钛、镍、铂中的一种或其组合。
本发明通过衬底预处理的方式,得到纳米级微尺寸结构的图形化衬底,在图形化衬底上生长的铅盐薄膜会继承衬底图形使得铅盐薄膜表面具有粗化形貌。通过人为在铅盐薄膜表面形成的纳米级微尺寸图形成为光线散射中心,此结构化的表面特征在于光线波长的尺度可使光线的折射及反射的方式无法由斯涅尔定律(Snell'sLaw)来预测,因而产生随机干扰效应,提高铅盐探测器的吸光率。该制备方法简单,性能理想,响应灵敏度高,具有广阔的应用前景。
附图说明
图1是原始衬底的示意图;
图2是图形化衬底的示意图;
图3是在图形化衬底上沉积铅盐薄膜的示意图;
图4是在铅盐薄膜沉积钝化层的示意图;
图5是在铅盐化合物薄膜上通过光刻剥离工艺制备金属电极层之后的铅盐红外探测器芯片结构示意图;
图6是铅盐红外探测器制备流程图;
在所有附图中,相同的附图标记用来表示相同的元件或结构,其中:1为图形化衬底,2为铅盐化合物薄膜,3为金属电极层,4为钝化层。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
一种铅盐红外探测器芯片结构及其制备方法,本实施方式中选择以硫化铅红外探测器为例,如图5所示,从下至上包括图形化衬底、硫化铅薄膜、钝化层和金属电极层,制作方法包括如下步骤:
1)衬底预处理:选取普通光学玻璃衬底,本实施中选取普通商用的光学玻璃。第一步用丙酮溶液超声清洗3分钟;第二步用无水乙醇溶液超声清洗3分钟;第三步用去离子水超声清洗2分钟;第四步用氮气吹干清洗完成之后的衬底以便于后续加工。
2)图形化衬底制备:第一步设计出金属电极层与沉积硫化铅薄膜的区域,并在沉积硫化铅薄膜的区域设计一定周期性结构的微结构图形阵列,并制成光刻版1。第二步在清洗完成的衬底上均匀涂抹一层PMMA光刻胶,涂抹时间90秒,匀胶机转速6000转/分钟,涂抹厚度300nm,接着,在170℃下烘烤2分钟。第三步使用紫外光刻机将光刻版1的图案转移至已经旋涂PMMA光刻胶的衬底上,曝光时间5s,并通过显影暴露出待加工区域。第四步用质量浓度10%-20%的氢氟酸腐蚀衬底表面并通过湿化学方法去掉PMMA光刻胶,此时衬底表面形成纳米级微尺寸形貌。第五步清洗基片表面残留杂质,清洗过程依次为丙酮溶液超声清洗3分钟,无水乙醇溶液超声清洗3分钟,去离子水超声清洗2分钟,最后用氮气吹干。
3)沉积硫化铅薄膜:以乙酸铅作为铅源,硫脲作为硫源,采用化学浴沉积法制备硫化铅反应溶液。具体地,称取0.025mol乙酸铅、0.075mol硫脲、0.05mol柠檬酸三钠,0.18mol氢氧化钾,将反应物溶解于加入250ml水的烧杯中,将清洗之后的图形化衬底放入烧杯中,将烧杯放入保温至40℃的水浴锅中进行反应。两小时后取出基板,获得继承了图形化衬底微结构形貌的硫化铅薄膜。清洗基片表面残留杂质,清洗过程依次为丙酮溶液超声清洗3分钟,无水乙醇溶液超声清洗3分钟,去离子水超声清洗2分钟,最后用氮气吹干。
4)沉积钝化层:第一步设计出钝化层位置并制成光刻版2;第二步在硫化铅薄膜上均匀涂抹一层PMMA光刻胶,涂抹时间90秒,匀胶机转速6000转/分钟,涂抹厚度300nm,接着,在170℃下烘烤2分钟。第三步使用紫外光刻机将光刻版2的图案转移至已经旋涂PMMA光刻胶的基板上,曝光时间5s,并通过显影暴露出钝化层区域。第四步使用等离子体增强化学的气相沉积(PECVD)方式在硫化铅薄膜表面蒸镀一层20nm厚的二氧化硅钝化层,并通过湿化学方法去掉PMMA光刻胶,此时获得继承了图形化衬底微结构形貌的钝化层。第五步清洗基片表面残留杂质,清洗过程依次为丙酮溶液超声清洗3分钟,无水乙醇溶液超声清洗3分钟,去离子水超声清洗2分钟,最后用氮气吹干。
5)金属电极层制备:第一步设计出电极位置并制成光刻版3;第二步在钝化层表面均匀涂抹一层PMMA光刻胶,涂抹时间90秒,匀胶机转速6000转/分钟,涂抹厚度300nm,接着,在170℃下烘烤2分钟。第三步使用紫外光刻机将光刻版3的图案转移至已经旋涂PMMA光刻胶的基板上,曝光时间5s,并通过显影暴露出电极区域。第四步使用电子束蒸镀的方式蒸镀一层铝电极,并通过湿化学方法去掉PMMA光刻胶,此时获得完整的芯片结构。第五步清洗基片表面残留杂质,清洗过程依次为丙酮溶液超声清洗3分钟,无水乙醇溶液超声清洗3分钟,去离子水超声清洗2分钟,最后用氮气吹干,完成硫化铅红外探测器芯片制备。
综上所述,本发明是一种铅盐红外探测器及其制备方法,本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种铅盐红外探测器芯片结构,自下而上依次包括:图形化衬底、铅盐化合物薄膜、钝化层和金属电极层,其特征在于:图形化衬底上生长的铅盐化合物薄膜、钝化层会依次继承图形化衬底的图形。
2.根据权利要求1所述的一种铅盐红外探测器芯片结构,其特征在于:图形化衬底的基材选自玻璃、陶瓷、硅和蓝宝石中的任意一种;所述图形化衬底是指在衬底沉积铅盐薄膜部分制备纳米级微尺寸图形,剩余制备金属电极部分不做处理,其中沉积铅盐薄膜部分图形的排列为规则有序分布的图形,或是不规则无序分布的图形,或者是能够达到增加光吸收,减少全反射的任意形状。
3.根据权利要求1所述的一种铅盐红外探测器芯片结构,其特征在于:铅盐化合物薄膜为PbS、PbSe、PbTe或对红外光有响应的其它铅盐化合物。
4.根据权利要求1所述的一种铅盐红外探测器芯片结构,其特征在于:钝化层为As2S3、CdTe、ZnSe、Al2O3、MgF2和SiO2中的一种。
5.根据权利要求1所述的一种铅盐红外探测器芯片结构,其特征在于:金属电极层为金、银、铝、铬、钛、镍、铂中的一种或其组合。
6.如权利要求1-5任一所述铅盐红外探测器芯片结构的制备方法,其特征在于,包括以下步骤:
1)衬底预处理:将衬底放入丙酮溶液中超声清洗,然后再用无水乙醇溶液超声清洗,接着用去离子水超声清洗,最后用氮气吹干备用;
2)在预处理后的衬底表面指定位置加工出纳米级微尺寸形貌,形成图形化衬底;
3)在图形化衬底上沉积铅盐化合物薄膜,此时铅盐化合物薄膜的形貌会继承图形化衬底的形貌;
4)在铅盐化合物薄膜表面生长钝化层;
5)采用光刻剥离工艺在铅盐化合物薄膜上制备金属电极层,完成芯片制备。
7.根据权利要求6所述的制备方法,其特征在于,图形化衬底的图形加工方式为湿法腐蚀、干法刻蚀、机械摩擦或其它可以达到同样纳米级微尺寸的方法中的任一项。
8.根据权利要求6所述的制备方法,其特征在于,沉积铅盐化合物薄膜的方法为化学浴沉积、化学气相沉积、物理气相沉积、原子层沉积、连续离子层吸附、电化学沉积、溶胶-凝胶法中的任一项。
9.根据权利要求6所述的制备方法,其特征在于,制备金属电极层的方法为电子束蒸发或磁控溅射方式。
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