CN112582486A - 一种NiO紫外光电探测器及其制备方法 - Google Patents

一种NiO紫外光电探测器及其制备方法 Download PDF

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CN112582486A
CN112582486A CN202011468770.0A CN202011468770A CN112582486A CN 112582486 A CN112582486 A CN 112582486A CN 202011468770 A CN202011468770 A CN 202011468770A CN 112582486 A CN112582486 A CN 112582486A
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杨为家
符跃春
王凤鸣
姚娟
何鑫
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Wuyi University
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Abstract

本发明公开了一种NiO紫外光电探测器及其制备方法，所述NiO紫外光电探测器包括由下至上排列的衬底、NiO薄膜、二氧化硅薄膜和金属电极，所述二氧化硅薄膜上通过光刻腐蚀出若干个凹槽，每个凹槽内竖直插设有NiO柱，所述二氧化硅薄膜的上表面涂覆有碳纳米管形成碳纳米网格，所述NiO柱的周围和碳纳米网格的上表面涂覆AlN纳米晶，并在AlN纳米晶的表面包覆金属量子点，所述金属电极溅射在AlN纳米晶的表面。本发明制备的NiO紫外光电探测器具有尺寸可控、分布均匀性好、综合性能优良的优点；采用无掩膜光刻技术，可以大幅度节约成本，相对于传统技术节省2‑10％的成本。

Description

一种NiO紫外光电探测器及其制备方法
技术领域
本发明涉及紫外光探测器技术领域，特别涉及一种NiO紫外光电探测器及其制备方法。
背景技术
紫外探测器在导弹预警、导弹制导、环境监测、保密通讯、空间探测等方面具有非常广阔的应用前景，是当前探测器领域研究的一个重要方向。
目前，用于制备紫外探测器的半导体材料主要有GaN、AlN、SiC、金刚石、BN、NiO、ZnO、Ga2O3等。GaN、AlN、SiC、金刚石、BN、Ga2O3等半导体基紫外探测器，通常是利用外延的方法制备，工艺复杂程度高，成本投入非常大，产业化技术难关多，距离商业化应用还有相当漫长的道路。因此，低成本、便于产业化的新型紫外探测器是人们不懈追求的目标。
NiO响应度高、探测范围广且化学稳定性好，而且生产成本也较低，是一种制备紫外探测的理想材料。研究人员开展了大量的研究，并取得了不错的进展。有研究人员以NiO纳米线为光敏层，制备了紫外探测器(ZL201410567389.8)。部分研究人员则提出了非极性p-NiO/n-ZnO异质结构紫外探测器(ZL201310038167.2)。进一步发展出了p-NiO/n-ZnO:Al结构紫外探测器(ZL201611208996.0)。优化地，在薄膜器件的基础上，有人提出利用聚苯乙烯微球为模板制备有序多孔ZnO/NiO异质结构薄膜(ZL201410653509.6)。然而，NiO基紫外探测依然有三个个问题需要解决：一是异质结构中的ZnO需要寻找一种性能更好、更加稳定的替代材料；二是NiO纳米材料的规则分布以及制备工艺需要改善，需要朝更加符合工业化生产的需求发展；三是NiO紫外探测器的性能需要进一步提升，满足日益复杂的应用环境。所以需要寻找一种能够解决上述问题的紫外探测器。
发明内容
本发明的目的在于：针对上述存在的问题，提供一种基于AlN纳米晶、碳纳米管、金属量子点协同增强的NiO紫外光电探测器，具有尺寸可控、分布均匀性好、综合性能优良的优点。
为了实现上述发明目的，本发明采用的技术方案如下：
一种NiO紫外光电探测器，包括由下至上排列的衬底、NiO薄膜、二氧化硅薄膜和金属电极，所述二氧化硅薄膜上通过光刻腐蚀出若干个凹槽，每个凹槽内竖直插设有NiO柱，所述二氧化硅薄膜的上表面涂覆有碳纳米管形成碳纳米网格，所述NiO柱的周围和碳纳米网格的上表面涂覆AlN纳米晶，并在AlN纳米晶的表面包覆金属量子点，所述金属电极溅射在AlN纳米晶的表面。
进一步地，所述NiO柱为正方形的NiO微米柱或NiO纳米柱，该NiO柱的边长为300nm-10μm，高度为500nm-10μm。
进一步地，所述AlN纳米晶的直径为2-50nm。
进一步地，所述金属量子点为Au、Pt、Ag，尺寸为0.5-2nm。
一种NiO紫外光电探测器的制备方法，包括以下步骤：
(1)NiO柱的制备：将NiO喷涂在衬底上形成NiO薄膜，在NiO薄膜的基础上，采用磁控溅射制备一层二氧化硅薄膜，然后采用无掩膜曝光技术，在二氧化硅层上确定生长NiO柱的区域，再采用湿法腐蚀，去除二氧化硅，在NiO薄膜上获得生长NiO柱的区域，然后采用气相外延的方法在NiO薄膜上获得生长NiO柱；
(2)碳纳米管的涂覆：将步骤(1)制备好的NiO柱样品转移至旋涂仪，在样品中心位置滴加碳纳米管溶液，旋涂分布均匀；
(3)AlN纳米晶的涂覆：在步骤(2)的基础上，在样品中心位置滴加AlN纳米晶溶液，通过旋涂仪旋涂均匀后，采用红外线低温烘干，接着重复进行AlN纳米晶的涂覆；
(4)退火处理：使用快速退火炉在真空或者保护气氛下退火处理，使AlN纳米晶、碳纳米管与NiO柱形成良好的键合；
(5)金属量子点的制备：采用喷金仪在样品表面溅射Pt或Au或Ag纳米粒子形成金属量子点，包覆在AlN纳米晶的表面；
(6)电极的制备：采用无掩膜光刻技术，获得制备电极的区域，然后采用热蒸镀技术在样品上制备金属电极。
进一步地，在步骤(1)中，所述NiO柱为NiO微米/纳米柱，所述NiO柱为正方形，其边长为300nm-10μm，高度为500nm-10μm，所述二氧化硅薄膜的厚度为10-30nm。
进一步地，在步骤(2)中，所述碳纳米管溶液的添加量为4-10滴，所述旋涂为先采用500-1000转/分的速率进行旋涂60-120s，使碳纳米管在样品上均匀铺开；进而采用2000-3500转/分的速率旋涂60-120s，使碳纳米管均匀分布在样品上，且在高速旋涂的过程中，适当补充4-8滴碳纳米管溶液。
进一步地，在步骤(3)中，所述AlN纳米晶溶液的添加量为4-10滴，所述旋涂为采用500-800转/分的速率进行旋涂60-120s，使AlN纳米晶溶液在样品上均匀铺开；进而采用2500-3000转/分的速率旋涂60-120s，使AlN纳米晶均匀分布在样品上；在高速旋涂的过程中，适当补充4-8滴AlN纳米晶溶液，所述涂覆次数为3-5次。
进一步地，在步骤(4)中，所述退火温度为350-900℃下，退火处理时间为30-120分钟。
进一步地，在步骤(5)中，所述金属量子点溅射时间为5-10s，溅射距离为5-10cm，溅射电流为80-100mA，金属量子点的尺寸为0.5-2nm。
综上所述，由于采用了上述技术方案，本发明的有益效果是：
(1)本发明采用AlN纳米晶、碳纳米管、金属量子点协同增强NiO紫外光电探测器，一方面，AlN纳米晶、碳纳米管均可以吸收紫外光，有利于拓展吸收波段，提高吸收效率；另一方面，碳纳米管具有优异的导电性能，可以作为光生载流子的快速收集体和快速传输通道；与此同时，金属量子点具有局域表面增强效应，且可以快速收集体，将光生载流子从半导体迅速提取到表面，有望较大幅度提升器件的响应速率和灵敏度。
(2)本发明采用无掩膜光刻技术，可以大幅度节约成本，相对于传统技术节省2-10％的成本。
(3)本发明的探测器采用NiO纳米材料的规则性强，分布均匀，有利于提高产品的均一性。
附图说明
图1是本发明的NiO紫外光电探测器的制备流程图。
图2是本发明所采用的碳纳米管的TEM图。
图3是应用本发明的方法制备的NiO紫外光电探测器的截面示意图。
附图中，10衬底、11NiO薄膜、12SiO2薄膜、13NiO柱、14碳纳米管网络、15AIN纳米晶、16金属电极。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚明白，以下举出优选实施例，对本发明进一步详细说明。然而，需要说明的是，说明书中列出的许多细节仅仅是为了使读者对本发明的一个或多个方面有一个透彻的理解，即便没有这些特定的细节也可以实现本发明的这些方面。
实施例1
一种NiO紫外光电探测器，包括由下至上排列的衬底、NiO薄膜、二氧化硅薄膜和金属电极，所述二氧化硅薄膜上通过光刻腐蚀出若干个凹槽，每个凹槽内竖直插设有NiO柱，所述二氧化硅薄膜的上表面涂覆有碳纳米管形成碳纳米网格，所述NiO柱的周围和碳纳米网格的上表面涂覆AlN纳米晶，并在AlN纳米晶的表面包覆金属量子点，所述金属电极溅射在AlN纳米晶的表面。其中NiO柱为正方形的NiO微米柱或NiO纳米柱，该NiO柱的边长为300nm，高度为500nm；AlN纳米晶的直径为2nm；金属量子点为Au、Pt、Ag，尺寸为0.5nm。
实施例2
一种NiO紫外光电探测器，包括由下至上排列的衬底、NiO薄膜、二氧化硅薄膜和金属电极，所述二氧化硅薄膜上通过光刻腐蚀出若干个凹槽，每个凹槽内竖直插设有NiO柱，所述二氧化硅薄膜的上表面涂覆有碳纳米管形成碳纳米网格，所述NiO柱的周围和碳纳米网格的上表面涂覆AlN纳米晶，并在AlN纳米晶的表面包覆金属量子点，所述金属电极溅射在AlN纳米晶的表面。其中NiO柱为正方形的NiO微米柱或NiO纳米柱，该NiO柱的边长为10μm，高度为10μm；AlN纳米晶的直径为50nm；金属量子点为Au、Pt、Ag，尺寸为2nm。
实施例3
一种NiO紫外光电探测器，包括由下至上排列的衬底、NiO薄膜、二氧化硅薄膜和金属电极，所述二氧化硅薄膜上通过光刻腐蚀出若干个凹槽，每个凹槽内竖直插设有NiO柱，所述二氧化硅薄膜的上表面涂覆有碳纳米管形成碳纳米网格，所述NiO柱的周围和碳纳米网格的上表面涂覆AlN纳米晶，并在AlN纳米晶的表面包覆金属量子点，所述金属电极溅射在AlN纳米晶的表面。其中NiO柱为正方形的NiO微米柱或NiO纳米柱，该NiO柱的边长为1μm，高度为1μm；AlN纳米晶的直径为30nm；金属量子点为Au、Pt、Ag，尺寸为1nm。
实施例4
本实施例的生长基于AlN纳米晶、碳纳米管、金属量子点协同增强的NiO紫外光电探测器的制备方法，包括以下步骤：
(1)NiO微米/纳米柱的制备：在NiO薄膜的基础上，采用磁控溅射制备一层厚度为10nm的二氧化硅。然后采用无掩膜曝光技术(无掩膜光刻机)，在二氧化硅层上获得生长NiO微米/纳米柱的区域。接着，采用湿法腐蚀，去除二氧化硅，在NiO薄膜上获得生长NiO微米/纳米柱的区域。然后，采用气相外延的方法，在NiO薄膜上获得生长NiO微米/纳米柱。NiO微米/纳米柱为正方形，其边长为300nm，高度为500nm。
(2)碳纳米管的涂覆：将步骤(1)制备好的NiO微米/纳米柱样品转移至旋涂仪，在样品中心位置滴加4滴碳纳米管溶液。采用1000转/分的速率进行旋涂60s，使碳纳米管在样品上均匀铺开；进而采用3500转/分的速率旋涂60s，使碳纳米管均匀分布在样品上。在高速旋涂的过程中，适当补充4滴碳纳米管溶液。
(3)AlN纳米晶的涂覆：在步骤(2)的基础上，旋涂AlN纳米晶溶液。具体工艺如下：首先，在样品中心位置滴加4滴AlN纳米晶溶液。采用800转/分的速率进行旋涂60s，使AlN纳米晶溶液在样品上均匀铺开；进而采用3000转/分的速率旋涂60s，使AlN纳米晶均匀分布在样品上。在高速旋涂的过程中，适当补充4滴AlN纳米晶溶液。之后，采用红外线低温烘干，接着进行第二次AlN纳米晶的涂覆。涂覆次数为3次。
(4)退火处理：使用快速退火炉在真空或者保护气氛下在350℃下退火处理120分钟，使AlN纳米晶、碳纳米管与NiO微米/纳米柱形成良好的键合。
(5)金属量子点的制备：采用喷金仪在样品表面溅射Pt或Au或Ag纳米粒子(量子点)，溅射时间为5s，溅射距离为5cm，溅射电流为100mA。金属量子点的尺寸为0.5nm。
(6)电极的制备：采用无掩膜光刻技术，获得制备电极的区域，然后采用热蒸镀技术在样品上制备金属电极。从而获得结构完整的基于AlN纳米晶、碳纳米管、金属量子点协同增强的NiO紫外光电探测器。
实施例5
本实施例的生长基于AlN纳米晶、碳纳米管、金属量子点协同增强的NiO紫外光电探测器的制备方法，包括以下步骤：
(1)NiO微米/纳米柱的制备：在NiO薄膜的基础上，采用磁控溅射制备一层厚度为30nm的二氧化硅。然后采用无掩膜曝光技术(无掩膜光刻机)，在二氧化硅层上获得生长NiO微米/纳米柱的区域。接着，采用湿法腐蚀，去除二氧化硅，在NiO薄膜上获得生长NiO微米/纳米柱的区域。然后，采用气相外延的方法，在NiO薄膜上获得生长NiO微米/纳米柱。NiO微米/纳米柱为正方形，其边长为10μm，高度为10μm。
(2)碳纳米管的涂覆：将步骤(1)制备好的NiO微米/纳米柱样品转移至旋涂仪，在样品中心位置滴加4-10滴碳纳米管溶液。采用500转/分的速率进行旋涂120s，使碳纳米管在样品上均匀铺开；进而采用2000转/分的速率旋涂120s，使碳纳米管均匀分布在样品上。在高速旋涂的过程中，适当补充8滴碳纳米管溶液。
(3)AlN纳米晶的涂覆：在步骤(2)的基础上，旋涂AlN纳米晶溶液。具体工艺如下：首先，在样品中心位置滴加10滴AlN纳米晶溶液。采用500转/分的速率进行旋涂120s，使AlN纳米晶溶液在样品上均匀铺开；进而采用2500转/分的速率旋涂120s，使AlN纳米晶均匀分布在样品上。在高速旋涂的过程中，适当补充8滴AlN纳米晶溶液。之后，采用红外线低温烘干，接着进行第二次AlN纳米晶的涂覆。涂覆次数为3-5次。
(4)退火处理：使用快速退火炉在真空或者保护气氛下在900℃下退火处理30分钟，使AlN纳米晶、碳纳米管与NiO微米/纳米柱形成良好的键合。
(5)金属量子点的制备：采用喷金仪在样品表面溅射Pt或Au或Ag纳米粒子(量子点)，溅射时间为10s，溅射距离为5cm，溅射电流为100mA。金属量子点的尺寸为2nm。
(6)电极的制备：采用无掩膜光刻技术，获得制备电极的区域，然后采用热蒸镀技术在样品上制备金属电极。从而获得结构完整的基于AlN纳米晶、碳纳米管、金属量子点协同增强的NiO紫外光电探测器。
实施例6
本实施例的生长基于AlN纳米晶、碳纳米管、金属量子点协同增强的NiO紫外光电探测器的制备方法，包括以下步骤：
(1)NiO微米/纳米柱的制备：在NiO薄膜的基础上，采用磁控溅射制备一层厚度为20nm的二氧化硅。然后采用无掩膜曝光技术(无掩膜光刻机)，在二氧化硅层上获得生长NiO微米/纳米柱的区域。接着，采用湿法腐蚀，去除二氧化硅，在NiO薄膜上获得生长NiO微米/纳米柱的区域。然后，采用气相外延的方法，在NiO薄膜上获得生长NiO微米/纳米柱。NiO微米/纳米柱为正方形，其边长为1μm，高度为1μm。
(2)碳纳米管的涂覆：将步骤(1)制备好的NiO微米/纳米柱样品转移至旋涂仪，在样品中心位置滴加6滴碳纳米管溶液。采用8000转/分的速率进行旋涂100s，使碳纳米管在样品上均匀铺开；进而采用3000转/分的速率旋涂100s，使碳纳米管均匀分布在样品上。在高速旋涂的过程中，适当补充6滴碳纳米管溶液。
(3)AlN纳米晶的涂覆：在步骤(2)的基础上，旋涂AlN纳米晶溶液。具体工艺如下：首先，在样品中心位置滴加8滴AlN纳米晶溶液。采用600转/分的速率进行旋涂80s，使AlN纳米晶溶液在样品上均匀铺开；进而采用2800转/分的速率旋涂80s，使AlN纳米晶均匀分布在样品上。在高速旋涂的过程中，适当补充6滴AlN纳米晶溶液。之后，采用红外线低温烘干，接着进行第二次AlN纳米晶的涂覆。涂覆次数为4次。
(4)退火处理：使用快速退火炉在真空或者保护气氛下在600℃下退火处理60分钟，使AlN纳米晶、碳纳米管与NiO微米/纳米柱形成良好的键合。
(5)金属量子点的制备：采用喷金仪在样品表面溅射Pt或Au或Ag纳米粒子(量子点)，溅射时间为8s，溅射距离为8cm，溅射电流为90mA。金属量子点的尺寸为1nm。
(6)电极的制备：采用无掩膜光刻技术，获得制备电极的区域，然后采用热蒸镀技术在样品上制备金属电极。从而获得结构完整的基于AlN纳米晶、碳纳米管、金属量子点协同增强的NiO紫外光电探测器。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种NiO紫外光电探测器，其特征在于，包括由下至上排列的衬底、NiO薄膜、二氧化硅薄膜和金属电极，所述二氧化硅薄膜上通过光刻腐蚀出若干个凹槽，每个凹槽内竖直插设有NiO柱，所述二氧化硅薄膜的上表面涂覆有碳纳米管形成碳纳米网格，所述NiO柱的周围和碳纳米网格的上表面涂覆AlN纳米晶，并在AlN纳米晶的表面包覆金属量子点，所述金属电极溅射在AlN纳米晶的表面。
2.根据权利要求1所述的一种NiO紫外光电探测器，其特征在于，所述NiO柱为正方形的NiO微米柱或NiO纳米柱，该NiO柱的边长为300nm-10μm，高度为500nm-10μm。
3.根据权利要求1所述的一种NiO紫外光电探测器，其特征在于，所述AlN纳米晶的直径为2-50nm。
4.根据权利要求1所述的一种NiO紫外光电探测器，其特征在于，所述金属量子点为Au、Pt、Ag，尺寸为0.5-2nm。
5.一种如权利要求1-4任一所述的NiO紫外光电探测器的制备方法，其特征在于，包括以下步骤：
(1)NiO柱的制备：将NiO喷涂在衬底上形成NiO薄膜，在NiO薄膜的基础上，采用磁控溅射制备一层二氧化硅薄膜，然后采用无掩膜曝光技术，在二氧化硅层上确定生长NiO柱的区域，再采用湿法腐蚀，去除二氧化硅，在NiO薄膜上获得生长NiO柱的区域，然后采用气相外延的方法在NiO薄膜上获得生长NiO柱；
(2)碳纳米管的涂覆：将步骤(1)制备好的NiO柱样品转移至旋涂仪，在样品中心位置滴加碳纳米管溶液，旋涂分布均匀；
(3)AlN纳米晶的涂覆：在步骤(2)的基础上，在样品中心位置滴加AlN纳米晶溶液，通过旋涂仪旋涂均匀后，采用红外线低温烘干，接着重复进行AlN纳米晶的涂覆；
(4)退火处理：使用快速退火炉在真空或者保护气氛下退火处理，使AlN纳米晶、碳纳米管与NiO柱形成良好的键合；
(5)金属量子点的制备：采用喷金仪在样品表面溅射Pt或Au或Ag纳米粒子形成金属量子点，包覆在AlN纳米晶的表面；
(6)电极的制备：采用无掩膜光刻技术，获得制备电极的区域，然后采用热蒸镀技术在样品上制备金属电极。
6.根据权利要求5所述的一种NiO紫外光电探测器的制备方法，其特征在于：在步骤(1)中，所述NiO柱为NiO微米/纳米柱，所述NiO柱为正方形，其边长为300nm-10μm，高度为500nm-10μm，所述二氧化硅薄膜的厚度为10-30nm。
7.根据权利要求5所述的一种NiO紫外光电探测器的制备方法，其特征在于：在步骤(2)中，所述碳纳米管溶液的添加量为4-10滴，所述旋涂为先采用500-1000转/分的速率进行旋涂60-120s，使碳纳米管在样品上均匀铺开；进而采用2000-3500转/分的速率旋涂60-120s，使碳纳米管均匀分布在样品上，且在高速旋涂的过程中，适当补充4-8滴碳纳米管溶液。
8.根据权利要求5所述的一种NiO紫外光电探测器的制备方法，其特征在于：在步骤(3)中，所述AlN纳米晶溶液的添加量为4-10滴，所述旋涂为采用500-800转/分的速率进行旋涂60-120s，使AlN纳米晶溶液在样品上均匀铺开；进而采用2500-3000转/分的速率旋涂60-120s，使AlN纳米晶均匀分布在样品上；在高速旋涂的过程中，适当补充4-8滴AlN纳米晶溶液，所述涂覆次数为3-5次。
9.根据权利要求5所述的一种NiO紫外光电探测器的制备方法，其特征在于：在步骤(4)中，所述退火温度为350-900℃下，退火处理时间为30-120分钟。
10.根据权利要求5所述的一种NiO紫外光电探测器的制备方法，其特征在于：在步骤(5)中，所述金属量子点溅射时间为5-10s，溅射距离为5-10cm，溅射电流为80-100mA，金属量子点的尺寸为0.5-2nm。
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