CN111244207B - 一种宽波段自供电锑薄膜光电探测器 - Google Patents
一种宽波段自供电锑薄膜光电探测器 Download PDFInfo
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Abstract
本发明公开了一种宽波段自供电锑薄膜光电探测器，由锑薄膜和银电极复合而成，所述锑薄膜是通过Sb粉气相沉积于衬底制得。本发明由通过Sb粉气相沉积于衬底制得的锑薄膜和银电极复合而成，锑薄膜质量高，连续性好，且制作工艺简单，省略了锑薄膜与基底材料的再复合工序，得到的光电探测器具备自供能特性和宽波段工作特性，且当所用衬底为柔性衬底时，得到的柔性光电探测器还具备优异的机械柔韧性。
Description
技术领域
本发明属于光电材料技术领域，涉及一种宽波段自供电锑薄膜光电探测器。
背景技术
光电探测器是一种能把光信号转换成电信号的装置。随着技术文明的发展，新型光电探测器在光电显示、成像、环境监测、光通信、军事、安全等诸多领域发挥着重要作用。而伴随着由石墨烯为代表的二维材料的出现，应用二维材料所制成的一系列性能优越的光电探测器将成为新型光电器件不可或缺的一部分。而研究人员对于这一类光电探测器的研究主要极中于以下几个方面：一方面，研究人员倾向于开发自驱动自供电的光电探测器，该探测器可在零偏置电压下工作，不消耗外部电力。与传统的需要消耗能源和电力的设备相比，它们具有极高的成本效益，可以直接应用于光电子***。另一方面，建立在轻质和可弯曲的基底上的柔性器件，由于其在大面积可折叠显示器、曲面数字电话等柔性电子***中的巨大应用潜力，近年来受到越来越多的关注。此外，具备宽波段响应的光电探测器也具有很大的实际意义。然而，尽管应用二维材料制成的光电探测器的优势是巨大的，但同时所面临的挑战也是巨大的。首先，通过转移等方法制备出的探测器件由于材料与衬底之间的接触的限制，使得所制备的光电探测器在稳定性以及性能上都受到了很大的制约。此外，由于衬底与生长材料之间的晶格匹配问题，使得在柔性衬底上制备出大面积高质量的薄膜材料面临很大的困难。最后，多功能光电探测器的制备往往伴随着繁琐而复杂的工艺，这无疑也为其大规模应用带来了巨大的阻碍。
发明内容
为了解决现有技术中存在的问题，本发明的目的是在于提供了一种宽波段自供电锑薄膜光电探测器，由通过Sb粉气相沉积于衬底制得的锑薄膜和银电极复合而成，具备自供能特性和宽波段工作特性，且当所用衬底为柔性衬底时，得到的柔性光电探测器还具备优异的机械柔韧性。
为了实现上述技术目的，本发明采用如下技术方案：
一种宽波段自供电光电探测器，由锑薄膜和银电极复合而成，所述锑薄膜是通过Sb粉气相沉积于衬底制得。
优选的方案，所述锑薄膜的具体制备过程为：将Sb粉置于加热区，将石英管内气压抽至10pa，并使用氩氢混合气体洗气15min～20min，保持气体流速为80～100sccm，让所述加热区温度以20～25℃/min由室温上升至440℃，将SiO2/Si衬底PI衬底放置于距离加热区中心14～15cm处，使得气化后的Sb粉沉积于衬底上得到所述锑薄膜。
优选的方案，所述锑薄膜的厚度为10～20nm。
优选的方案，所述Sb粉的纯度不低于99.99％。
优选的方案，所述衬底为SiO2/Si刚性衬底或PI柔性衬底。
更优选的方案，所述SiO2/Si刚性衬底先采用食人鱼溶液进行浸泡并且超声5h，之后使用超纯水清洁，高温干燥后使用；所述PI柔性衬底先使用无水乙醇浸泡并超声2h，之后经超纯水清洗后干燥使用。
与现有技术相比，本发明的优势在于：
1、本发明通过气相沉积制得的锑薄膜，由扫描电子显微镜SEM图和光学显微镜OM图可知，其具有良好的连续性、极大的表面积、良好的晶体构结，且分布致密均匀，具有微米级别的横向尺寸；由X射线衍射(XRD)图谱和拉曼光谱可知，其具有单晶结构的存在，具有高纯度以及高连续性特性；同时制备成的薄膜可以直接沉积在衬底上，省略了薄膜与基底材料的再复合工序，以方便下一步的器件合成，简化了制作工艺，具有很好的应用前景。
2、本发明先通过气相沉积方法直接在SiO2/Si衬底上制备锑薄膜，然后再将薄膜与银电极复合形成光电探测器，在0偏置电压的情况下，制备的光电探测器仍能够十分稳定的工作，具有不错的响应，且在405nm、450nm、660nm和1060nm的激光激发下，所制备的锑薄膜光电探测器都具备良好且稳定的响应，是一种具备自供能特性和宽波段工作特性的光电探测器。
3、本发明先通过气相沉积方法直接在PI柔性衬底上制备锑薄膜，然后再将薄膜与银电极复合形成柔性光电探测器，在受到不同程度的弯曲应力时，仍能够稳定的工作，具有良好的稳定性，且锑薄膜柔性光电探测器在经过200次弯折之后，I-t特性曲线几乎没有受到影响，预示了锑薄膜和柔性光电探测器具备优异的机械柔韧性。
附图说明
图1为气相沉积法制备Sb薄膜的***结构示意简图；
图2为锑薄膜原子结构简图(a)、SEM图(b)、SiO2/Si衬底上的锑薄膜的光学显微镜图(c)和PI衬底上的锑薄膜的光学显微镜图(d)；
图3为锑薄膜的XRD图谱(a)以及Raman测试图谱(b)；
图4为实施例3制得的光电探测器的结构简图(a)及实施例4制得的柔性光电探测器的结构简图(b)；
图5为实施例3制得的光电探测器的I-V(a)特性曲线和I-t特性曲线图(b)；
图6为不同波长激光激发下的实施例3制得的光电探测器的工作特性曲线图；
图7为不同波长激光激发下的实施例4制得的柔性光电探测器的工作特性曲线图；
图8为不同曲率半径曲面下实施例4制得的柔性光电探测器的I-t特性曲线图；
图9为抗弯折测试后的实施例4制得的柔性光电探测器的I-t特性曲线图；
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件制造商建议的条件进行，其光电探测器和柔性光电探测器通过常规的方法制得。所用试剂仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本发明中柔性光电探测器固定在不同曲率半径的平面上，再通过Keithly2600***表征其工作性能特性。
本发明中柔性光电探测器件经过不同次数的弯折之后，通过keithly2600***表征其工作性能特性。
实施例1
首先将尺寸为1×1cm SiO2/Si(300nm)衬底置于食人鱼溶液中，浸泡超声处理五小时以清除其表面杂质，然后将所处理后的SiO2/Si衬底浸泡至无水乙醇溶液中继续超声处理30分钟以去除其表面食人鱼溶液及杂质残留物，最后将处理后的衬底使用超纯水进一步超声清洁，最后将步骤2-3重复三次后处理后的衬底高温干燥后获得干净的300nm SiO2/Si衬底。
将0.0765g Sb粉末置于加热区，使用真空泵将石英管内气压抽至10pa左右状态，并使用氩氢混合气体洗气15min～20min，保持气体流速为100sccm，让所述加热区温度以20℃/min由室温上升至440℃，保持15min，使所述锑粉气化；将SiO2/Si衬底放置于距离加热中心14～16cm处，使得气化后所述锑粉粉末沉积于SiO2/Si衬底上得到所述锑薄膜，其厚度为12～15nm。
实施例2
首先将尺寸为1.5×2cm PI衬底置于无水乙醇溶液中，浸泡超声处理2小时以清除其表面杂质，然后将所处理后的SiO2/Si衬底浸泡至超纯水中继续超声处理30分钟以上以进一步去除其表面杂质，最后将步骤1-2重复三次后将处理后的衬底干燥而得到干净的PI衬底；
将0.0782g Sb粉末置于加热区，使用真空泵将石英管内气压抽至10pa左右状态，并使用氩氢混合气体洗气15min～20min，保持气体流速为100sccm，让所述加热区温度以20℃/min由室温上升至440℃，保持15min，使所述锑粉气化；将PI衬底放置于距离加热中心14～16cm处，使得气化后所述锑粉粉末沉积于PI衬底上得到所述锑薄膜，其厚度为16～18nm。
实施例3
将实施例1中所制备的沉积于Sb-SiO2衬底上的锑薄膜置于操作平台，然后使用银胶作为电极并按照如图4(a)所示结构点制电极，构成一个锑薄膜光电探测器，最后将导线与银电极复合后接入测试平台进行测试。
实施例4
将实施例2中所制备的沉积于PI衬底上的锑薄膜置于操作平台，然后使用银胶作为电极并按照如图4(b)所示结构点制电极，构成一个锑薄膜柔性光电探测器，最后将导线与银电极复合后接入测试平台进行测试。
如图2所示，(a)表示Sb的原子结构图像；(b)表示Sb的扫描电子显微镜SEM图像；(c)表示Sb于SiO2/Si衬底上的光学显微镜OM图像；(d)表示Sb于PI柔性衬底上的光学显微镜OM图像；由(b)证实所获得的锑薄膜具有良好的晶体构结，且分布致密均匀，具有微米级别的横向尺寸，(c)和(d)中的光学显微镜图像进一步确认了这一结论，而由光学图像可知，在两种衬底上所沉积的锑薄膜都具有良好的连续性以及极大的表面积。
综上所述，我们成功地获得了少层的锑薄膜。并且具有良好的晶体结构和微米级别的横向尺寸。
如图3所示，(a)为锑薄膜的X射线衍射(XRD)图谱，锑薄膜分别在003与006处出现了衍射峰，以上结构确认了锑薄膜中单晶结构的存在，以及薄膜成分的高纯度特性，XRD的测试结果说明了我们所制备的薄膜的高质量以及高连续性特性；
(b)为锑薄膜与的拉曼光谱(由633nm激光激发)，通过使用来自SiO2/Si衬底的主要散射峰在520cm-1处固定拉曼的校准标准。在大约115.7cm-1和152.31cm-1处的两个峰分别归因于Sb晶体的Eg和Alg振动模式，表明通过气相沉积法成功制备了锑薄膜。
如图5所示，(a)显示出了在不同偏压下锑薄膜光电探测器的I-V特性曲线，其中光源功率强度保持在100mW，激光波长为450nm。相较于无光照时的暗电流曲线，光电流增益明显且光电流大小随着偏压的升高而增加，整体I-V曲线呈现一个典型的非线性关系，说明在电极与锑薄膜之间形成了良好的肖特基接触。值得注意的一点是，对于加正偏压与负偏压时的I-V特性曲线而言，其对应的曲线是不对称的，这是由于在电极与电极之间存在一个不对称的肖特基势垒，使得探测器在加正向偏置与反向偏置的时候的工作特性曲线出现了不同。(b)显示出了锑薄膜光电探测器的I-t特性曲线，在0偏置电压的情况下，制备的锑薄膜光电探测器仍能够十分稳定的工作，且具有不错的响应，探测器在零偏置电压工作时光电流增益可达0.535μA，上升时间为6.12s，下降时间为26.4ms，该结果预示了本发明得锑薄膜光电探测器是一种具备自供能特性的光电探测器；
如图6所示，为锑薄膜光电探测器在不同波长激光激发下的特性曲线，表示在405nm；450nm；1060nm的激光激发下，所制备的锑薄膜光电探测器都具备良好且稳定的响应。以上结果验证了所制备的锑薄膜光电探测器的宽波段工作特性。
如图7所示，为锑薄膜柔性光电探测器在不同波长激光激发下的特性曲线，表示在405nm；450nm；660nm；1060nm的激光激发下，所制备的锑薄膜柔性光电探测器都具备良好且稳定的响应。以上结果验证了所制备的锑薄膜柔性光电探测器的宽波段工作特性。
如图8所示，为锑薄膜柔性光电探测器在不同弯曲程度下的特性曲线，通过使用具有不同曲率半径的曲面材料，我们在各种弯曲状态下测试了锑薄膜柔性光电探测器，锑薄膜柔性光电探测器在不同曲率半径下的I-t特性曲线表明，在受到不同程度的弯曲应力时，我们的锑薄膜柔性探测器仍能够稳定的工作，但由于在受到弯曲时，光照区域相应的也发生了变化，所以对光电流增益而言，不同的曲率半径对其具有一定的影响。这是由于对于完全程度越大的表面而言，受到激光照射的区域相应的减小，使得器件受到光照的有效面积减小，从而减小了所产生的光生电子空穴对，降低了光电流增益。
如图9所示，为了验证我们的锑薄膜柔性光电探测器的机械柔韧性，展示了锑薄膜柔性光电探测器在不同次数的弯折测试之后的工作特性曲线，由图中的特性曲线可知，锑薄膜柔性光电探测器在经过200次弯折之后，I-t特性曲线几乎没有受到影响，该结果预示了锑薄膜柔性光电探测器具备优异的机械柔韧性。
Claims (3)
1.一种宽波段自供电锑薄膜光电探测器，其特征在于：由锑薄膜和银电极复合而成，所述锑薄膜是通过Sb粉气相沉积于衬底制得；
所述锑薄膜的具体制备过程为：将Sb粉置于加热区，将石英管内气压抽至10pa，并使用氩氢混合气体洗气15min～20min，保持气体流速为100sccm，让所述加热区温度以20℃/min由室温上升至440℃，保持15min，将衬底放置于距离加热区中心14～15cm处，使得气化后的Sb粉沉积于衬底上得到所述锑薄膜；
所述锑薄膜的厚度为16~18nm；
所述衬底为PI柔性衬底。
2.根据权利要求1所述的宽波段自供电锑薄膜光电探测器，其特征在于：所述Sb粉的纯度不低于99.99％。
3.根据权利要求1所述的宽波段自供电锑薄膜光电探测器，其特征在于：所述PI柔性衬底先使用无水乙醇浸泡并超声2h，之后经超纯水清洗后干燥使用。
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