CN106206829B - 一种基于锰掺杂氮化铜薄膜的可见光探测器 - Google Patents
一种基于锰掺杂氮化铜薄膜的可见光探测器 Download PDFInfo
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Abstract
本发明属于光电探测技术领域,提供一种基于锰掺杂氮化铜薄膜的可见光探测器。所述的可见光探测器由衬底1、底电极2、可见光吸收层3和顶电极4组成,可见光探测器为最简单的三明治结构,可见光吸收层3为锰掺杂氮化铜薄膜,位于底电极2和顶电极4之间。其制造方法为,首先将透明导电玻璃刻蚀,形成0.8cm宽的透明导电窄条,然后利用磁控溅射技术沉积锰掺杂氮化铜薄膜,最后用磁控溅射或者蒸发蒸镀的方法沉积金属顶电极4,便得到基于锰掺杂氮化铜薄膜的可见光探测器。该可见光探测器拥有良好的光响应度、持久可重复跳变性能、快速的响应时间,且结构简单,制作成本低,原料丰富易得,制造方法简单,采用磁控溅射和蒸镀技术,可以规模化生产。
Description
技术领域
本发明属于光电探测技术领域,具体涉及一种可见光探测器。
背景技术
可见光探测器在科学技术工业领域有着广泛的应用,包括光学成像、通信传感和环境监测等。因此探索新材料应用于可见光探测器具有十分重要的意义。可见光探测器就是对可见光进行探测的一种器件,对于性能稳定的器件,通常在没有光照的情况下,在探测器两个电极上加上电压,所测得的电流大小为一个恒定值,当用可见光照射探测器时,在相同的电压下,电流会急剧增加,再一次撤掉光照,电流会降低到原始大小。并且光电流会随着可见光强度的增加而增加,可见光探测器便是通过检测在一定电压下电流的变化来判断周围可见光强度变化的器件。
由于过渡金属氮化物特殊的电学的、光学的、磁学的和催化的特性,在下一代电子学和光电子学已经显示出潜在应用价值。作为一种具有巨大潜力的过渡金属氮化物,氮化铜拥有和Cu(In,Ga)Se2半导体相似的耐缺陷特性和合适的可见光吸收特性,以及较低的功函数、自限制的表面氧化和缺陷迁移的稳定性,这使得氮化铜薄膜可以成为在太阳能电池和可见光探测器领域具有前景的耐缺陷光吸收材料。并且,Cu和N元素是环境友好型的丰富资源,原料易得,无需复杂的化学工艺流程,因此低成本的氮化铜材料在纳米电子学和光电子学上有着显著的优势。直到现在,许多的研究都集中于制备掺杂的氮化铜薄膜,并探索了其光存储、阻变存储、自旋电子学和催化剂等方面的应用。但是令人惊讶的是,尽管许多研究者发现了氮化铜薄膜优异的光学特性,基于氮化铜的光探测器并没有报道。
本发明提供了一种基于氮化铜薄膜的可见光探测器及其制备方法,所述可见光充分体现了氮化铜的光电特性,且制备方法简单,原料和工业成本低,可批量生产等优点。
发明内容
鉴于现有技术中存在上述技术问题,本发明提供一种基于锰掺杂氮化铜薄膜的可见光探测器及其制备方法。锰掺杂氮化铜薄膜在外加电压作用下,在可见光照射与暗态下的电流大小不同且易于分辨,暗态电流变化到光照电流以及光照电流恢复到暗态电流的反应时间极短,灵敏度高,并且可以多次重复此性能,尤其适合用于可见光探测器。
本发明采用的技术方案如下所述:
本发明所述的基于锰掺杂氮化铜薄膜的可见光探测器的基本结构主要分为四层,依次包括衬底、底电极、可见光吸收层和顶电极;其中,所述可见光吸收层为锰掺杂氮化铜薄膜。
所述锰掺杂氮化铜薄膜采用双靶共溅射制备,厚度为50-300nm。
所述衬底为透明电子玻璃或者载玻片;
所述底电极为透明导电薄膜,如:FTO、ITO、AZO等;
所述顶电极为金属材料,如:Au、Ag、Cu、Al、Pt、Ti等。
本发明所述的可见光探测器为最简单的三明治结构,可见光吸收层3为锰掺杂氮化铜薄膜,位于底电极2和顶电极4之间。
本发明还提供所述的锰掺杂氮化铜薄膜的可见光探测器的制备方法,具体步骤为:
a.在透明导电薄膜上,用稀盐酸和锌粉进行刻蚀,制得导电层,作为底电极;
b.清洗并烘干上述衬底,并以此作为基片,采用双靶共溅射制备锰掺杂氮化铜薄膜,得到可见光吸收层;
c.直接在上述基片的可见光吸收层上,通过溅射靶材或蒸发蒸镀制备顶电极。
其中,所述衬底为透明电子玻璃或者载玻片;所述底电极为透明导电薄膜,如:FTO、ITO、AZO等;所述顶电极为金属材料,如:Au、Ag、Cu、Al、Pt、Ti等。
其中,底电极的宽度为0.8cm;锰掺杂氮化铜薄膜厚度约为50-300nm;顶电极的厚度为100nm。
在上述步骤b中,锰掺杂氮化铜薄膜的制备过程为:将基片放置于真空度优于5.0×10-4Pa的环境中,采用高纯度的铜靶材和锰靶材在通入氮气和氩气的氛围中进行共溅射,制得锰掺杂氮化铜薄膜。
在上述步骤c中,顶电极的制备过程为:将样品放置于真空度为5.0×10-4Pa的环境中,再通入纯氩气,通过溅射靶材进行电极的制备,或者转入高真空环境的蒸发室进行电极的沉积。
本发明的关键之一在于用制备出锰掺杂氮化铜薄膜,制备时可以采用纯度高达99.999%的铜靶材和99.97%的锰靶材以及99.999%的氮气和氩气,在高真空的实验条件下通入溅射气体和反应气体,衬底必须清洗干净,可分别经过去离子水、丙酮和酒精超声清洗20min。
由于氮化铜薄膜在不同的实验条件下制备,会表现出不同的性质,从导体到半导体最后到绝缘体的氮化铜薄膜都有,探索合适的条件制备出具有可见光相应的氮化铜薄膜,在此基础上用于掺杂锰金属,最后得到锰掺杂氮化铜薄膜可见光探测器。
基于氮化铜薄膜的可见光探测器将会是氮化铜光电应用的一个重要进步。为了获得比纯氮化铜薄膜更优异的光学性能,我们选择了锰作为掺杂剂来改善氮化铜薄膜的可见光响应,因为据报道锰掺杂能改善量子点和染料敏化太阳能电池的光吸收性能。同时锰掺杂氮化铜薄膜出现了特别的光电特性,在光学带隙增加了0.2eV的同时,其电阻急剧增加,有效地减少了氮化铜内存在的自由载流子的数量,这有利于光生载流子对导电性的贡献。
本发明中可见光吸收层采用的锰掺杂氮化铜薄膜,该薄膜材料还具有耐缺陷特性和合适的可见光吸收特性,以及较低的功函数、自限制的表面氧化和缺陷迁移的稳定性,且原材料丰富易得。该薄膜的可见光吸收特性体现在具有适合可见光吸收的带隙,对可见光敏感,可通过吸收可见光产生光生载流子,从而使得电流增大。
拥有良好的探测性能才能拥有实际的应用价值,采用电化学工作站对制备好的可见光探测器性能测试,选定好测试电压范围,以免损坏器件,控制好测试条件对于获得优异性能的探测器至关重要。本发明方法具有如下有益效果:1、所述可见光探测器拥有对可见光敏感、光响应度高、响应速度快、重复性强、工作电压低、低能耗、无运动部件等优点,且结构简单、体积小;2、利用成熟的磁控溅射技术和蒸发蒸镀技术,成本低,原料丰富易得,制造方法简单,成膜质量好,可以规模化生产;3、锰掺杂氮化铜薄膜稳定性好、易于保存,具有较高的实用价值。
附图说明
图1是本发明的结构原理图;
图2是本发明的可见光响应的性能测试图;
图2(a)为锰掺杂氮化铜薄膜可见光探测器的I-t曲线;
图2(b)中放大显示了电流上升时间和恢复时间。
图中有:1、衬底,2、底电极,3、光吸收层,4、顶电极。
具体实施方式
以下结合实例对本发明进行详细说明,但是应当知道的是,本发明不受这些实例所限。
实施例1;
本发明制备的锰掺杂氮化铜薄膜为半导体薄膜材料,其具体过程为:
a.首先用稀硝酸和Zn粉刻蚀FTO导电玻璃;
b.然后分别在去离子水、丙酮和酒精中超声20min,用氮气吹干,放置于磁控溅射室的基片架上,接下来采用直流磁控溅射制备200nm厚的氮化铜薄膜和锰掺杂氮化铜薄膜;铜靶材的尺寸为两英寸的直径、5mm厚度,纯度为99.999%;溅射气体和反应气体分别为99.999%的Ar和N2;靶基距为80mm,铜靶溅射功率为80W,真空度优于5×10-4Pa,溅射气压为0.9Pa;锰靶材和铜靶材同时溅射,锰靶材为纯度为99.97%,直径2英寸,厚度3mm,采用射频溅射源,溅射功率为40W,其他条件和铜靶溅射条件一样;
c.锰掺杂氮化铜薄膜制备好以后,取出样品放置于真空蒸镀腔室,进行Ag电极的制备,所采用的电极材料为纯度99.99%的Ag颗粒;Ag电极的厚度为100nm,采用自行设计的掩膜版,使得电极和薄膜接触的有效面积为2×2mm2。
可见光检测器的器件结构如图1所示,最终形成了Ag/Mn-Cu3N/FTO/glass的三明治器件结构。
如附图1所示为我们所制备的基于氮化铜薄膜的可见光探测器的结构,在玻璃基底(1)上是刻蚀的FTO(2),接着是通过磁控溅射方法制备的氮化铜薄膜或者锰掺杂氮化铜薄膜(3),顶层部分代表着Ag电极(4)。测试可见光探测器性能时接通Ag电极和FTO电极,可见光从透明导电层FTO一侧照射。
锰掺杂可见光探测器性能测试,首先要在一定的电压范围内测试伏安特性曲线,本发明测试了电压-4到4V范围内的电流变化,分为两种环境,在没有可见光照射时的伏安特性曲线和在一定可见光照射下的伏安特性曲线,根据结果选取电流变化最大时的电压进行I-t性能测试,测试I-t曲线是为了解探测器的可见光响应度、可重复性和响应速度,这是探测器最为关键的性能,对于探测器的实用性至关重要。本发明利用电化学工作站进行探测器性能测试,电化学工作站集成了多种测试手段,可进行探测器的I-V曲线和I-t性能测试,选用生活中常见的手电筒作为可见光源,可见光源的辐射照度通过光度计测得。本发明锰掺杂可见光探测器通过测试伏安特性曲线和I-t性能,如附图2所示,该探测器在室温大气环境中拥有良好的光响应度、持久可重复跳变性能、快速的响应时间,表明本发明拥有可靠的实用价值和应用前景。其中图2(a)为锰掺杂氮化铜薄膜可见光探测器的I-t曲线,反映了在无光照和光照条件下的可见光响应特性以及可见光响应的可重复性能,(b)图中放大显示了电流上升时间和恢复时间,反应了探测器的响应速度。
实施例2
本发明制备的锰掺杂氮化铜薄膜为半导体薄膜材料,其具体过程为:
a.首先用稀硝酸和Zn粉刻蚀FTO导电玻璃;
b.然后分别在去离子水、丙酮和酒精中超声20min,用氮气吹干,放置于磁控溅射室的基片架上,接下来采用直流磁控溅射制备50nm厚的氮化铜薄膜和锰掺杂氮化铜薄膜;铜靶材的尺寸为两英寸的直径、5mm厚度,纯度为99.999%;溅射气体和反应气体分别为99.999%的Ar和N2;靶基距为80mm,铜靶溅射功率为80W,真空度优于5×10-4Pa,溅射气压为0.9Pa;锰靶材和铜靶材同时溅射,锰靶材为纯度为99.97%,直径2英寸,厚度3mm,采用射频溅射源,溅射功率为40W,其他条件和铜靶溅射条件一样;
c.制备好锰掺杂氮化铜薄膜,无需取出薄膜样品,直接将溅射室的真空抽至5.0×10-4Pa,再通入纯度为99.999%的氩气,流量为66sccm,溅射压强为0.5Pa,溅射时间为5min,通过溅射高纯度的银靶材(99.99%)进行Ag电极的制备;Ag电极的厚度为100nm。
实施例3
本发明制备的锰掺杂氮化铜薄膜为半导体薄膜材料,其具体过程为:
a.首先用稀硝酸和Zn粉刻蚀FTO导电玻璃;
b.然后分别在去离子水、丙酮和酒精中超声20min,用氮气吹干,放置于磁控溅射室的基片架上,接下来采用直流磁控溅射制备300nm厚的氮化铜薄膜和锰掺杂氮化铜薄膜;铜靶材的尺寸为两英寸的直径、5mm厚度,纯度为99.999%;溅射气体和反应气体分别为99.999%的Ar和N2;靶基距为80mm,铜靶溅射功率为80W,真空度优于5×10-4Pa,溅射气压为0.9Pa;锰靶材和铜靶材同时溅射,锰靶材为纯度为99.97%,直径2英寸,厚度3mm,采用射频溅射源,溅射功率为40W,其他条件和铜靶溅射条件一样;
c.制备好锰掺杂氮化铜薄膜,无需取出薄膜样品,直接将溅射室的真空抽至5.0×10-4Pa,再通入纯度为99.999%的氩气,流量为66sccm,溅射压强为0.5Pa,溅射时间为5min,通过溅射高纯度的银靶材(99.99%)进行Ag电极的制备;Ag电极的厚度为100nm。
Claims (10)
1.一种基于锰掺杂氮化铜薄膜的可见光探测器,该探测器器主要分为四层,依次包括:衬底、底电极、可见光吸收层和顶电极,其特征在用于,所述可见光吸收层为锰掺杂氮化铜薄膜。
2.如权利要求1所述的可见光探测器,其特征在于:所述锰掺杂氮化铜薄膜采用双靶共溅射制备。
3.如权利要求1所述的可见光探测器,其特征在于:所述衬底为透明电子玻璃或者载玻片;所述底电极为透明导电薄膜;所述顶电极为金属材料。
4.如权利要求3所述的可见光探测器,其特征在于:所述透明导电薄膜为FTO、ITO或AZO;所述金属材料为Au、Ag、Cu、Pt、Al或Ti。
5.如权利要求1所述的可见光探测器,其特征在于:所述可见光吸收层的厚度为厚度为50-300nm,所述顶电极的厚度为100nm。
6.一种如权利要求1所述的可见光探测器的制备方法,其特征在于,所述制备方法的具体步骤为:
a.在衬底上,用稀盐酸和锌粉进行刻蚀,制得导电层,作为底电极;
b.清洗并烘干上述衬底,并以此作为基片,采用双靶共溅射制备锰掺杂氮化铜薄膜,得到可见光吸收层;
c.直接在上述基片的可见光吸收层上,通过溅射靶材或蒸发蒸镀制备顶电极。
7.如权利要求6所述的制备方法,其特征在于:所述衬底为透明电子玻璃或者载玻片;所述底电极为透明导电薄膜;所述顶电极为金属材料。
8.如权利要求6所述的制备方法,其特征在于:底电极的宽度为0.8cm;锰掺杂氮化铜薄膜厚度为50-300nm;顶电极的厚度为100nm。
9.如权利要求6所述的制备方法,其特征在于:在上述步骤b中,锰掺杂氮化铜薄膜的制备过程为:将基片放置于真空度优于5.0×10-4Pa的环境中,采用铜靶材和锰靶材在通入氮气和氩气的氛围中进行共溅射,制得锰掺杂氮化铜薄膜。
10.如权利要求6所述的制备方法,其特征在于:在上述步骤c中,顶电极的制备过程为:将样品放置于真空度为5.0×10-4Pa的环境中,再通入纯氩气,通过溅射靶材进行电极的制备,或者转入高真空环境的蒸发室进行电极的沉积。
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