CN106847989B - 基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器及方法 - Google Patents
基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器及方法 Download PDFInfo
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Abstract
本发明公开了一种基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器及其制备方法。本发明以细金属丝作为基底,在其表面沿垂直方向生长氧化锌纳米棒阵列,然后在氧化锌纳米棒阵列表面上均匀覆盖一层聚乙烯咔唑薄层,之后在其外表面包裹单层石墨烯薄膜,其中夹杂一根细银丝引出电极。本发明解决了传统纤维状探测器内部界面接触差的问题,并且用面接触的表面电极取代线接触的表面电极,提高了探测器性能。
Description
技术领域
本发明涉及紫外探测技术领域,特别是一种基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器及其制备方法。
背景技术
随着摩登电子时代的发展,比如电子皮肤、可伸缩电路器件等柔性可穿戴的电子器件在我们日常生活中起到了越来越大的作用。由于纤维本身具有轻质、柔韧并且容易编织的特点,纤维状的能源器件已经被广泛研究,包括纤维状超级电容器、锂电池和太阳能电池等,但是这些能源器件主要是为了相应的功能性器件服务,比如显示、照明、监测和传感等。传感器是信息传输很重要的一部分,而光探测器作为传感器的一员,在军事探测、生物传感、光通信等方面已经有着极为广泛的应用。因此,柔性可编织的纤维状探测器也急需研究,但其中存在的问题也很明显,就是纤维的曲面结构,增加了器件功能层的接触缺陷,这极大影响了器件性能。而传统的纯无机结构功能层以及使用的线状外电极使得这一缺陷更加严重,这从Ko等(Nanoscale,2015,7,2735-421)和Zhang等(ACS Nano,2013,7,4537-4544)已有的研究结果中就可以看出来。因此,迫切需要研究出一种能够优化接触界面的纤维状紫外光探测,而现有的技术还没有利用界面优化这样的方式解决纤维状光电子器件中存在的接触缺陷问题。
发明内容
本发明的目的在于提供一种基于界面优化的纤维状紫外光探测器及其制备方法,以期可以有效地提高纤维状探测器的响应速度、开关比等性能。
实现本发明目的的技术解决方案为:本发明提供的基于界面优化的纤维状紫外光探测器,由在低功函数的金属丝基底上生长的氧化锌纳米棒阵列作为光导层,外面覆盖一层有机聚合物聚乙烯咔唑(PVK)用来平滑阵列表面,形成紧密接触且形成PN结有利于驱动光生载流子的分离与传输,最外层包裹大面积的单层石墨烯薄膜作为表面电极,同时引出一根与石墨烯直接接触的细银丝导线便于应用。
本发明提供的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器的制备方法,具体步骤为:
(1)取功函数较低的细金属丝,分别用去离子水跟无水乙醇超声清洗30分钟并干燥,然后用原子层沉积技术在金属丝表面沉积一定厚度的氧化锌薄膜作为种子层,继而用水热法在种子层表面沿垂直方向生长氧化锌纳米棒阵列。
(2)将生长有氧化锌纳米棒阵列的金属丝浸泡在聚乙烯咔唑(PVK)的氯苯溶液中,浸泡一段时间后取出晾干,则在氧化锌阵列表面覆盖了一层平整光滑的聚乙烯咔唑(PVK)薄层。
(3)转移单层石墨烯薄膜浮于水面,将一根细银丝与上述表面有氧化锌阵列和聚乙烯咔唑功能化处理后的金属丝平行放置并固定好,继而从水中捞取石墨烯薄膜,并使使石墨烯薄膜将金属丝都包裹住,然后一定温度下烘干,器件便制备完成。
与已有技术相比,本发明的有益效果为:1)本发明使用氧化锌纳米棒阵列和聚乙烯咔唑(PVK)杂化相较于传统的纯无机纤维状探测器而言,其层与层之间的接触更为紧密,表面更为光滑,缺陷更少,对光生载流子的束缚会更少。2)本发明使用的单层石墨烯薄膜作为表面电极,与细金属丝表面的各功能层之间是面接触,这与传统缠绕金属丝电极形成的线接触相比,接触面积更大,更利于载流子传输。并且石墨烯因为超柔的特性,与功能层之间的接触更为紧密,接触缺陷更少,进一步提升了载流子的传输。最终使纤维状探测器获得更快的响应速度和更高的开关比。
附图说明
图1为本发明基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器的结构示意图,其中图(a)为全视图,图(b)为透视图。
图2为本发明中实施例1所制备的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器的微观结构SEM图。其中图(a)为制备的纤维状光探测器扫描电镜全视图,图(b)为石墨烯与聚乙烯咔唑层交界处的扫描电镜图,图(c)为氧化锌阵列表面的聚乙烯咔唑层的扫描电镜图,图(d)为氧化锌阵列与聚乙烯咔唑层截面的扫描电镜图,图(e)为制备的纤维状光探测器的侧视图,图(f)为石墨烯与聚乙烯咔唑层交界处放大的扫描电镜图。
图3为本发明中实施例1所制备的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器在无光和波长325nm的紫外光照射下的电流与电压关系特性曲线。
图4为本发明中实施例1所制备的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器在波长325nm、光能量为0.5mW/cm2的紫外光照射,偏压为-0.5V下不弯曲和弯曲5%条件下的光响应曲线。
图5为本发明中实施例2所制备的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器在无光和波长325nm的紫外光照射下的电流与电压关系特性曲线。
图6为本发明中实施例2所制备的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器在波长325nm、光能量为0.5mW/cm2的紫外光照射,偏压为-0.5V下的光响应曲线。
具体实施方式
结合附图,本发明的一种基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器,金属丝1作为基底,基底的表面沉积均匀致密的氧化锌薄膜2,氧化锌薄膜表面垂直方向生长有氧化锌纳米棒阵列3,氧化锌纳米棒阵列外表面包覆聚乙烯咔唑层4,聚乙烯咔唑层表面设置一根与金属丝衬底平行的银丝5,单层石墨烯薄膜设置在上述结构的最外层6。
所述金属丝包括银丝、铝丝、钛丝或锌丝,直径为0.1mm~1mm。
所述原子层沉积的氧化锌薄膜厚度为50nm~200nm。
所述氧化锌纳米棒阵列中氧化锌纳米棒的长度为500nm~4μm,直径为50nm~200nm,相邻氧化锌纳米棒的间距为50~150nm。
所述聚乙烯咔唑层厚度为100nm~300nm。
所述银丝的直径为25μm~100μm。
一种制造上述纤维状紫外光探测器的方法,包括以下步骤:
步骤1、分别用去离子水、无水乙醇对金属丝超声清洗并干燥,然后用原子层沉积方法在金属丝表面沉积氧化锌薄膜作为种子层,继而用水热法在种子层表面沿垂直方向生长氧化锌纳米棒阵列;
所述氧化锌薄膜的厚度为50nm~200nm;氧化锌纳米棒阵列中氧化锌纳米棒的长度为500nm~4μm,直径为50nm~200nm,相邻氧化锌纳米棒的间距为50~150nm;所述金属丝包括银丝、铝丝、钛丝或锌丝,直径为0.1mm~1mm。
步骤2、将生长有氧化锌纳米棒阵列的金属丝浸泡在聚乙烯咔唑的氯苯溶液中,浸泡后取出晾干,则在氧化锌纳米棒阵列表面覆盖了一层平整光滑的聚乙烯咔唑薄层;
所述聚乙烯咔唑的氯苯溶液浓度为10g/L~30g/L,浸泡时间2h~24h,晾干后薄膜厚度为100nm~300nm。
步骤3、转移单层石墨烯薄膜浮于水面,将一根银丝与上述处理后的金属丝平行放置并固定好,继而从水中捞取石墨烯薄膜,并使石墨烯薄膜将金属丝都包裹住,然后烘干,器件便制备完成。
所述银丝的直径为25μm~100μm,烘干温度为40~80℃。
本发明使用氧化锌纳米棒阵列和聚乙烯咔唑(PVK)杂化相较于传统的纯无机纤维状探测器而言,其层与层之间的接触更为紧密,表面更为光滑,缺陷更少,对光生载流子的束缚会更少。
下面结合实施例对本发明做进一步详细的描述。
实施例1
参见图1,本实施例基于一种界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器具有如下结构:以细金属丝作为基底,在基底的表面沉积有一层均匀致密的氧化锌薄膜,以氧化锌薄膜为种子层在金属丝基底的表面沿垂直方向生长有氧化锌纳米棒阵列,在上述纳米棒表面包覆一层聚乙烯咔唑(PVK),在PVK表面有一根与细金属丝衬底平行的细银丝,最后功能化的金属丝与细银丝被单层石墨烯薄膜紧紧包裹。
本实施例基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器的制备方法是按照如下步骤进行:
(1)取直径为0.5mm的锌丝,分别用去离子水、无水乙醇超声清洗30分钟并干燥,然后利用原子层沉积技术在金属锌丝表面沉积厚度为150nm厚度的氧化锌薄膜。之后进一步通过水热法在表面沿垂直方向生长氧化锌纳米棒阵列,氧化锌纳米棒的长度为3.5μm,直径为150nm。
(2)将生长有氧化锌纳米棒阵列的金属锌丝浸泡在聚乙烯咔唑(PVK)的氯苯溶液中,其浓度为10g/L,浸泡时间为12h,取出后晾干,在表面覆盖了平整的聚乙烯咔唑(PVK)薄层,其厚度为180nm。
(3)转移单层石墨烯薄膜浮于水面,将一根直径25μm细银丝与上述功能化处理后的金属丝平行放置并固定好,进一步从水中捞取石墨烯薄膜使其将金属丝都包裹住,然后50℃下烘干,器件便制备完成。
本实施例所制备的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器,其微观结构如图2所示。从图中可以看出,聚乙烯咔唑(PVK)在氧化锌阵列表面形成一层光滑平整的薄膜,超柔的石墨烯薄膜紧紧地包裹住功能化的金属丝。氧化锌纳米棒阵列与聚乙烯咔唑之间的界面接触、聚乙烯咔唑与石墨烯之间的界面接触都非常致密。
在无光下和325nm波段不同光强的紫外光照射下,探测器的电流与电压关系特性曲线如图3所示。从图中看出所制备的器件在无光条件下表现出典型整流特性,这是由于氧化锌与聚乙烯咔唑(PVK)形成的PN结造成的内建电场所导致。当波长为325nm光能量为0.05mW/cm2的紫外光照射时就产生了明显的光电流,体现了器件优越的光电探测特性。
图4为本实施例所制备的纤维状紫外光探测器在波长325nm、光能量为0.5mW/cm2的紫外光照射,偏压为-0.5V下不弯曲和弯曲5%条件下的光响应曲线;从图中可以看出器件很稳定,可重复地反映出对光的开关,并且体现了器件良好的柔性。
实施例2
参见图1,本实施例基于一种界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器具有如下结构:以细金属丝作为基底,在基底的表面沉积有一层均匀致密的氧化锌薄膜,以氧化锌薄膜为种子层在金属丝基底的表面沿垂直方向生长有氧化锌纳米棒阵列,在上述纳米棒表面包覆一层聚乙烯咔唑(PVK),在PVK表面有一根与细金属丝衬底平行的细银丝,最后功能化的金属丝与细银丝被单层石墨烯薄膜紧紧包裹。
本实施例基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器的制备方法是按照如下步骤进行:
(1)取直径为1mm的锌丝,分别用去离子水、无水乙醇超声清洗30分钟并干燥,然后利用原子层沉积技术在金属锌丝表面沉积厚度为100nm厚度的氧化锌薄膜。之后进一步通过水热法在表面沿垂直方向生长氧化锌纳米棒阵列,氧化锌纳米棒的长度为2μm,直径为100nm。
(2)将生长有氧化锌纳米棒阵列的金属锌丝浸泡在聚乙烯咔唑(PVK)的氯苯溶液中,其浓度为20g/L,浸泡时间为24h,取出后晾干,在表面覆盖了平整的聚乙烯咔唑(PVK)薄层,其厚度为250nm。
(3)转移单层石墨烯薄膜浮于水面,将一根直径100μm细银丝与上述功能化处理后的金属丝平行放置并固定好,进一步从水中捞取石墨烯薄膜使其将金属丝都包裹住,然后50℃下烘干,器件便制备完成。
本实施例所制备的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑(PVK)/石墨烯杂化的纤维状紫外光探测器,在无光下和325nm波段的紫外光照射下,探测器的电流与电压关系特性曲线如图5所示。从图中看出所制备的器件在无光条件下表现出典型整流特性,这是由于氧化锌与聚乙烯咔唑(PVK)形成的PN结造成的内建电场所导致。当波长为325nm、光能量0.5mW/cm2的紫外光照射时就产生了明显的光电流,体现了器件优越的光电探测特性。
图6为本实施例所制备的纤维状紫外光探测器在波长325nm、光能量为0.5mW/cm2的紫外光作为光源下的光响应曲线;从图中可以看出器件很稳定,可重复地反映出光的开关。
Claims (9)
1.一种基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器,其特征在于,金属丝(1)作为基底,基底的表面沉积均匀致密的氧化锌薄膜(2),氧化锌薄膜表面垂直方向生长有氧化锌纳米棒阵列(3),氧化锌纳米棒阵列外表面包覆聚乙烯咔唑层(4),聚乙烯咔唑层表面设置一根与金属丝衬底平行的银丝(5),单层石墨烯薄膜设置在上述结构的最外层(6);
所述氧化锌薄膜厚度为50nm~200nm。
2.根据权利要求1所述的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器,其特征在于,所述金属丝包括银丝、铝丝、钛丝或锌丝,直径为0.1mm~1mm。
3.根据权利要求1所述的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器,其特征在于,氧化锌纳米棒阵列中氧化锌纳米棒的长度为500nm~4μm,直径为50nm~200nm,相邻氧化锌纳米棒的间距为50~150nm。
4.根据权利要求1所述的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器,其特征在于,聚乙烯咔唑层厚度为100nm~300nm。
5.根据权利要求1所述的基于界面优化的氧化锌纳米棒阵列/聚乙烯咔唑/石墨烯杂化的纤维状紫外光探测器,其特征在于,银丝的直径为25μm~100μm。
6.一种制造权利要求1所述纤维状紫外光探测器的方法,其特征在于,包括以下步骤:
步骤1、分别用去离子水、无水乙醇对金属丝超声清洗并干燥,然后用原子层沉积方法在金属丝表面沉积氧化锌薄膜作为种子层,继而用水热法在种子层表面沿垂直方向生长氧化锌纳米棒阵列;
步骤2、将生长有氧化锌纳米棒阵列的金属丝浸泡在聚乙烯咔唑的氯苯溶液中,浸泡后取出晾干,则在氧化锌纳米棒阵列表面覆盖了一层平整光滑的聚乙烯咔唑薄层;
步骤3、转移单层石墨烯薄膜浮于水面,将一根银丝与上述处理后的金属丝平行放置并固定好,继而从水中捞取石墨烯薄膜,并使石墨烯薄膜将金属丝都包裹住,然后烘干,器件便制备完成。
7.根据权利要求6所述的方法,其特征在于,步骤1中氧化锌薄膜的厚度为50nm~200nm;氧化锌纳米棒阵列中氧化锌纳米棒的长度为500nm~4μm,直径为50nm~200nm,相邻氧化锌纳米棒的间距为50~150nm;所述金属丝包括银丝、铝丝、钛丝或锌丝,直径为0.1mm~1mm。
8.根据权利要求6所述的方法,其特征在于,步骤2中聚乙烯咔唑的氯苯溶液浓度为10g/L~30g/L,浸泡时间2h~24h,晾干后薄膜厚度为100nm~300nm。
9.根据权利要求6所述的方法,其特征在于,步骤3中银丝的直径为25μm~100μm,烘干温度为40~80℃。
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