CN105118887B - 一种铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关及其制备方法 - Google Patents
一种铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关及其制备方法,其是在绝缘衬底上表面分布有硒化锌纳米带,硒化锌纳米带的一端设置有与硒化锌纳米带呈欧姆接触的金电极,另一端设置有与硒化锌纳米带呈肖特基接触的石墨烯薄膜,在石墨烯薄膜的上表面修饰有呈六角点阵排布的铟纳米颗粒阵列。本发明中的蓝光光电开关通过利用排列规则的铟纳米颗粒阵列表面等离子体共振的特性,增强了对光的吸收,提高了对光的响应度;本发明制备方法简单,适合大规模生产,可制备响应速度快、抗电磁干扰强的蓝光光电开关,为硒化锌纳米材料在光电开关的应用中开拓了新的前景。
Description
技术领域
本发明属于半导体光电开关领域,具体涉及石墨烯/硒化锌纳米带肖特基结蓝光光电开关及其制备方法。
背景技术
蓝色光是一种波长范围在440nm~475nm的可见光,在日常生活中十分常见,蓝色也是三原色中的一元。光电开关,又被称为光电传感器,是光电接近开关的简称,它是利用被检测物对光束的遮挡或反射,由同步回路选通电路,从而检测物体的有无,光电开关将输入电流在发射器上转换为光信号射出,接收器再根据接收到的光线的强弱或有无对目标物体进行探测。蓝光光电开关就是采用蓝色光作为检测光束,对微弱的蓝光信号的检测是光电开关的关键技术。现有的光电开关中,纳米光电开关与同种材质的薄膜光电开关相比,具有更快的反应速度及抗干扰能力,因此纳米光电开关具有很好的发展前景及潜在意义,例如安防系统中常见的光电开关烟雾报警器,工业中常用的机械手臂运动次数计数器等。
表面等离子体是指在金属表面存在的自由振动的电子与光子相互作用产生的沿着金属表面传播的电子疏密波,它能够被电子也能被光波激发。表面等离子体是目前纳米光电子学科的一个重要的研究方向,它受到了包括材料学家,化学家,物理学家,生物学家等多个领域人士的极大的关注。随着纳米技术的发展,表面等离子体被广泛研究用于光子学,数据存储,显微镜,太阳能电池和生物传感器等方面。
硒化锌是一种重要的II-VI族化合物半导体材料,它在室温下的直接禁带宽度约为2.7eV,对波长为460nm的蓝光有很强的吸收。一直以来,硒化锌都被视为是光电器件领域前景广阔的纳米材料,并在发光二极管(LEDs)、激光二极管(LDs)等方面得到广泛应用。和传统的半导体材料硅和砷化镓相比,硒化锌对蓝光及紫外光更具有灵敏性。
石墨烯是由单层碳原子周期性紧密堆积构成的结构类似苯环(六角形蜂巢结构)的一种二维碳材料。石墨烯是由英国曼切斯特大学的两位科学家首次发现的,当时他们通过对石墨片层层剥离得到了仅由一层碳原子构成的薄片,就是石墨烯。石墨烯是已知的世上最薄、最坚硬的纳米材料,它几乎是完全透明的,只吸收2.3%的光;导热系数高达5300W/m·K,高于碳纳米管和金刚石,常温下其电子迁移率超过15000cm2/V·s,又比纳米碳管或硅晶体高,而电阻率只约10-8Ω·m,比铜或银更低,为世上电阻率最小的材料。由于其独有的特性,石墨烯被称为“神奇材料”,科学家甚至预言其将“彻底改变21世纪”。由于高导电性、高强度、超轻薄等特性,石墨烯在航天军工领域的应用优势也是极为突出的。美国NASA开发出应用于航天领域的石墨烯传感器,能很好的对地球高空大气层的微量元素、航天器上的结构性缺陷等进行检测,并且石墨烯在超轻型飞机材料领域的应用上也发挥了重要的作用。因其电阻率极低,电子迁移的速度极快,因此被期待可用来发展更薄、导电速度更快的新一代电子元件或晶体管。
发明内容
本发明是为避免上述现有技术所存在的不足之处,充分利用石墨烯这一新型的二维纳米材料,以及金属纳米颗粒特殊的等离子体共振特性,提供一种结构新颖、制备工艺简单、光吸收能力强、响应速度快、且抗电磁干扰能力强的一种铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关。
本发明为解决技术问题采用如下技术方案:
本发明铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,其特点在于:在绝缘衬底上表面分布有硒化锌纳米带,所述硒化锌纳米带的一端设置有与所述硒化锌纳米带呈欧姆接触的金电极,所述硒化锌纳米带的另一端设置有与所述硒化锌纳米带呈肖特基接触的石墨烯薄膜,在所述石墨烯薄膜的上表面修饰有呈六角点阵排布的铟纳米颗粒阵列,在所述石墨烯薄膜的一侧引出有与石墨烯薄膜呈欧姆接触的引出电极。金电极与石墨烯薄膜位于硒化锌纳米带的两侧,且通过硒化锌纳米带连通,两者彼此不接触;引出电极位于石墨烯薄膜上,与硒化锌纳米带不接触。
其中,所述硒化锌纳米带为本征硒化锌纳米带;所述石墨烯薄膜为本征石墨烯薄膜。
所述绝缘衬底是以单晶硅为基底、且二氧化硅层厚度不小于300nm的二氧化硅片。
所述金电极厚度为15-30nm。所述铟纳米颗粒阵列采用聚苯乙烯微球模板法制作而成,所用聚苯乙烯微球的直径为300-900nm。构成所述铟纳米颗粒阵列的各铟纳米颗粒直径为50-90nm。
本发明上述铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关的制备方法是按如下步骤进行:
(1)将二氧化硅片依次用丙酮、酒精超声10分钟,再用去离子水超声5分钟,然后用氮气枪吹干,获得绝缘衬底;
(2)通过刮蹭的方式将硒化锌纳米带转移到绝缘衬底上的绝缘层上,并来回刮蹭使硒化锌纳米带分布均匀;
(3)通过紫外光刻与电子束镀膜在硒化锌纳米带的一侧蒸镀金电极;
(4)通过气-液界面自组装法,在表面生长有石墨烯的铜箔上铺设具有六角密堆积结构的聚苯乙烯微球薄膜,作为生长六角铟纳米颗粒阵列的模板,具体步骤为:
a、实验准备:
a1、玻璃片表面清洗:为了改善玻璃片表面亲水性,需要对玻璃片进行表面处理,用由氨水、双氧水及去离子水按体积比1:1:5构成的混合溶液对玻璃片进行浸泡1~2h,然后取出并用去离子水清洗、吹干备用;
a2、配制聚苯乙烯微球溶液:滴取浓度为5%的聚苯乙烯微球原溶液,加入两倍体积的铺展剂乙醇,再进行超声分散处理,使聚苯乙烯微球充分融入乙醇,获得聚苯乙烯微球溶液;
b、实验操作:
b1、在玻璃片上滴两滴聚苯乙烯微球溶液,使溶液均匀铺展在玻璃片上;
b2、将玻璃片慢慢倾斜地放入水中,使小球在水面上自组装形成单层有序排列;
b3、再在水中添加表面活性剂十二烷基硫酸钠,使聚苯乙烯微球更加紧密排列;
b4、将生长有石墨烯的铜箔慢慢放入水中,用提拉法把聚苯乙烯微球排列转移到铜箔的上表面,然后让铜箔上水自然蒸发,聚苯乙烯微球就在石墨烯的上表面形成一层聚苯乙烯微球薄膜。
(5)利用热蒸发工艺在铺设有聚苯乙烯微球薄膜的铜箔上表面蒸镀厚度为50nm的铟膜,将表面镀有铟膜的铜箔置于温度为70℃的酒精中浸泡10分钟,再将其置于甲苯溶液中均匀搅拌,使得石墨烯的上表面修饰呈六角点阵排布的铟纳米颗粒阵列;
用刻蚀液将铜箔刻蚀掉,获得上表面修饰有呈六角点阵排布的铟纳米颗粒阵列的石墨烯薄膜;
(6)利用湿法转移将石墨烯薄膜转移到绝缘衬底上,使其位于硒化锌纳米带的另一侧,具体操作方法为:使用掩膜版进行紫外光刻,使得硒化锌纳米带的另一侧出现光刻图形(即图形处无光刻胶覆盖,其余部分有光刻胶覆盖),将石墨烯薄膜转移到绝缘衬底上,100℃烘干2h,利用石墨烯与二氧化硅较强的附着力,通过丙酮冲洗,去除光刻胶及位于光刻胶位置处的石墨烯,使图形位置处的石墨烯薄膜保留,即完成。
(7)在石墨烯薄膜上表面点上银浆作为引出电极,即完成铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带异质结蓝光光电开关的制备。
本发明的肖特基结蓝光光电开关是基于金属纳米颗粒(铟纳米颗粒)特殊的表面等离子共振特性,增强器件的光电特性,具体工作原理如下:在以硒化锌和石墨烯的肖特基结为核心的器件结构上功能性修饰均匀分布的铟纳米颗粒,利用铟纳米颗粒对特定波长光(即蓝光,波长约460nm)的吸收能力,结合硒化锌本身带隙决定的对光的吸收峰,从而最大程度的提高整个器件对蓝光的吸收能力。金属纳米颗粒由于其特殊的结构特性,金属颗粒内部与表面存在大量自由电子,形成自由电子气团,即等离子体。当入射光与金属纳米结构表面自由电子气团的振动发生共振时就形成了表面等离子体共振,在光谱上表现为一种强共振吸收峰。吸收的入射光与自由电子紧密结合形成局部化表面态电磁运动模式,被称为表面等离激元,这种特殊的电磁运动模式将吸收的入射光子不断地耦合到与之接触的石墨烯及纳米带当中,形成增强的光电流,进而增强器件的光电特性。本发明采用CVD方法制备的本征硒化锌纳米带及石墨烯薄膜,石墨烯为弱P型类金属材料,石墨烯与硒化锌形成肖特基异质结。本征硒化锌纳米带制备方法简单,条件容易控制,方便以后大规模生产。通过简单的表面修饰铟纳米颗粒,利用表面等离子体共振原理提高器件的光电特性,相比以往通过掺杂、特殊的器件结构的方法,本发明利用简单的策略,以达到提高器件性能的目的,是未来制备光电器件不错的途径。
与已有技术相比,本发明的有益效果体现在:
1、本发明通过简单的工艺方法制备了铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,既有硒化锌对蓝光的灵敏性和铟纳米颗粒阵列的表面等离子体共振特性,又结合了石墨烯高透光率、低电阻率等优良特性,制备出了高性能蓝光光电开关;
2、本发明采用气-液界面自组装法,在石墨烯基底表面铺上一层致密的六角密堆积的聚苯乙烯微球,作为后续试验的模板,大大提高了六角铟纳米颗粒阵列的有序度;
3、本发明利用聚苯乙烯微球模板法制备的六角铟纳米颗粒阵列,颗粒大小均一,间距一致,能够很好的增强颗粒附近的电场强度和提高对特定波长光的吸收能力,所得蓝光光电开关具有光吸收能力强、响应速度快等特点。
附图说明
图1为本发明铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关的结构示意图;
图2为本发明表面修饰有呈六角点阵排布的铟纳米颗粒阵列的石墨烯薄膜的结构示意图;
图3分别为本发明铟纳米颗粒阵列的SEM图(图3(a))和铟纳米颗粒阵列修饰石墨烯/硒化锌纳米带的SEM图(图3(b));
图4为本发明实施例中样品InNPs@Graphene/ZnSeNRs(图4(a))、样品Graphene/ZnSeNRs(图4(b))分别在黑暗和蓝光照射下的电流与电压关系特性曲线;
图5为本发明实施例中样品InNPs@Graphene/ZnSeNRs分别在黑暗和蓝光照射下的时间响应曲线,其中图5(a)为时间响应曲线,图5(b)表示上升时间(τr)与下降时间(τf);
图6为本发明实施例中样品Graphene/ZnSeNRs分别在黑暗和蓝光照射下的时间响应曲线,其中图6(a)为时间响应曲线,图6(b)表示上升时间(τr)与下降时间(τf);
图中标号:1为绝缘衬底;2为硒化锌纳米带;3为金电极;4为石墨烯薄膜;5为铟纳米颗粒阵列;6为引出电极。
具体实施方式:
实施例1
参见图1和图2,本实施例铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关具有如下结构:在绝缘衬底1上表面分布有硒化锌纳米带2,硒化锌纳米带2的一端设置有与硒化锌纳米带2呈欧姆接触的金电极3,硒化锌纳米带2的另一端设置有与硒化锌纳米带2呈肖特基接触的石墨烯薄膜4,在石墨烯薄膜4的上表面修饰有呈六角点阵排布的铟纳米颗粒阵列5,在石墨烯薄膜4的一侧引出有与石墨烯薄膜呈欧姆接触的引出电极6。
本实施例中铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关的制备方法是按如下步骤进行:
(1)将二氧化硅片依次用丙酮、酒精超声10分钟,再用去离子水超声5分钟,然后用氮气枪吹干,获得绝缘衬底;
(2)通过刮蹭的方式将硒化锌纳米带转移到绝缘衬底上,来回刮蹭使纳米带均匀分布;
(3)通过紫外光刻与电子束镀膜在硒化锌纳米带的一侧蒸镀金电极:利用掩膜板光刻工艺在绝缘层上刻出所需的电极图案,所用掩膜板为单电极掩膜板,以方便后续的二次光刻;采用电子束镀膜工艺在绝缘层上镀20nm金薄膜,并将镀有金薄膜的二氧化硅片置于丙酮中,以去除有光刻胶部分及其上附着的金薄膜,获得所需的金电极;
(4)通过气-液界面自组装法,在表面生长有石墨烯的铜箔上铺设具有六角密堆积结构的聚苯乙烯微球薄膜,作为生长六角铟纳米颗粒阵列的模板;具体步骤为:
a、实验准备:
a1、玻璃片表面清洗:为了改善玻璃片表面亲水性,需要对玻璃片进行表面处理,用氨水、双氧水及去离子水按体积比1:1:5构成的混合溶液对玻璃片进行浸泡1~2h,然后取出并用去离子水清洗、吹干备用;
a2、配制聚苯乙烯微球溶液:滴取浓度为5%的聚苯乙烯微球原溶液,加入两倍体积的铺展剂乙醇,再进行超声分散处理,使聚苯乙烯微球充分融入乙醇,获得聚苯乙烯微球溶液;
b、实验操作:
b1、在玻璃片上滴两滴聚苯乙烯微球溶液,使溶液均匀铺展在玻璃片上;
b2、将玻璃片慢慢倾斜地放入水中,使小球在水面上自组装形成单层有序排列;
b3、再在水中添加表面活性剂十二烷基硫酸钠,使聚苯乙烯微球更加紧密排列;
b4、将长有石墨烯的铜箔慢慢放入水中,用提拉法把聚苯乙烯微球排列转移到石墨烯的上表面,然后让铜箔上水自然蒸发,聚苯乙烯微球就在石墨烯上表面形成一层聚苯乙烯微球薄膜。
(5)利用热蒸发工艺在铺设有聚苯乙烯微球薄膜的铜箔上表面蒸镀厚度为50nm的铟膜,将表面镀有铟膜的铜箔置于温度为70℃的酒精中浸泡10分钟,再将其置于甲苯溶液中均匀搅拌,使得石墨烯的上表面修饰呈六角点阵排布的铟纳米颗粒阵列,其SEM图如图3(a)所示。
用刻蚀液将铜箔刻蚀掉,获得上表面修饰有呈六角点阵排布的铟纳米颗粒阵列的石墨烯薄膜;
(6)利用湿法转移将石墨烯薄膜转移到绝缘衬底上,使其位于硒化锌纳米带的另一侧;
(7)在石墨烯薄膜上表面点上银浆作为引出电极,即得铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带异质结蓝光光电开关,其SEM图如图3(b)所示,所得样品表示为InNPs@Graphene/ZnSeNRs。
为对比不同肖特基结蓝光光电开关的性能,做如下对比例:
按实施例1相同的方式制备石墨烯/硒化锌纳米带肖特基结蓝光光电开关,区别在于没有修饰铟纳米颗粒阵列,所得样品表示为Graphene/ZnSeNRs。
各样品在黑暗下(dark)和蓝光照射下(light)的电流与电压关系特性曲线如图4所示,各样品的时间响应图谱如图5和图6所示;
从图4中可以看出与Graphene/ZnSeNRs样品相比,InNPs@Graphene/ZnSeNRs样品在光照下电流有很大的提升。从图5和图6中可以看出InNPs@Graphene/ZnSeNRs样品具有较快的响应速度,有光照下,电流会迅速上升,关闭入射光,光电流迅速消失。通过截取上升和下降沿的10%到90%,计算可知修饰前后上升时间和下降时间分别0.92s/1.13s和0.07s/0.08s,可以看出修饰铟纳米颗粒阵列后,上升时间和下降时间都缩短了很多,这种通过修饰铟纳米颗粒阵列提高光电流强度及响应速度的制备方法为光电开关的发展开辟了新的途径。
铟纳米颗粒阵列修饰石墨烯使得器件的光电流有明显的提高,这是因为铟纳米颗粒在蓝光的照射下会发生表面等离子体共振的现象,并将光耦合进入纳米带当中,从而加强了对蓝光的吸收,提高了光电流的强度。
Claims (7)
1.一种铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,其特征在于:在绝缘衬底(1)上表面分布有硒化锌纳米带(2),所述硒化锌纳米带(2)的一端设置有与所述硒化锌纳米带(2)呈欧姆接触的金电极(3),所述硒化锌纳米带(2)的另一端设置有与所述硒化锌纳米带(2)呈肖特基接触的石墨烯薄膜(4),在所述石墨烯薄膜(4)的上表面修饰有呈六角点阵排布的铟纳米颗粒阵列(5),在所述石墨烯薄膜(3)的一侧引出有与石墨烯薄膜呈欧姆接触的引出电极(6)。
2.根据权利要求1所述的铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,其特征在于:所述硒化锌纳米带为本征硒化锌纳米带;所述石墨烯薄膜为本征石墨烯薄膜。
3.根据权利要求1所述的铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,其特征在于:所述绝缘衬底是以单晶硅为基底、且二氧化硅层厚度不小于300nm的二氧化硅片。
4.根据权利要求1所述的铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,其特征在于:所述金电极厚度为15-30nm。
5.根据权利要求1所述的铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,其特征在于:所述铟纳米颗粒阵列采用聚苯乙烯微球模板法制作而成,所用聚苯乙烯微球的直径为300-900nm。
6.根据权利要求1所述的铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关,其特征在于:构成所述铟纳米颗粒阵列的各铟纳米颗粒直径为50-90nm。
7.一种权利要求1-6中任意一项所述的铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带肖特基结蓝光光电开关的制备方法,其特征是按如下步骤进行:
(1)将二氧化硅片依次用丙酮、酒精超声10分钟,再用去离子水超声5分钟,然后用氮气枪吹干,获得绝缘衬底;
(2)通过刮蹭方式将硒化锌纳米带转移到绝缘衬底上;
(3)通过紫外光刻与电子束镀膜在硒化锌纳米带的一侧蒸镀金电极;
(4)通过气-液界面自组装法,在表面生长有石墨烯的铜箔上铺设具有六角密堆积结构的聚苯乙烯微球薄膜,作为生长铟纳米颗粒阵列的模板;
(5)利用热蒸发工艺在铺设有聚苯乙烯微球薄膜的铜箔上表面蒸镀厚度为50nm的铟膜,然后置于温度为70℃的酒精中浸泡10分钟,再置于甲苯溶液中均匀搅拌,使得石墨烯的上表面修饰呈六角点阵排布的铟纳米颗粒阵列;
通过刻蚀液将铜箔刻蚀掉,获得上表面修饰有呈六角点阵排布的铟纳米颗粒阵列的石墨烯薄膜;
(6)利用湿法转移将所述石墨烯薄膜转移到绝缘衬底上,使其位于硒化锌纳米带的另一侧;
(7)在石墨烯薄膜上表面点上银浆作为引出电极,即得铟纳米颗粒阵列修饰的石墨烯/硒化锌纳米带异质结蓝光光电开关。
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