CN115172489A - 一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件及其制备方法 - Google Patents
一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件及其制备方法 Download PDFInfo
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Abstract
一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件，包括支撑衬底、铁电二维钙钛矿、TMDs材料和两个源漏电极，所述铁电二维钙钛矿和TMDs材料铺设于支撑衬底上，所述铁电二维钙钛矿和TMDs材料相互重叠部分位于支撑衬底中部且TMDs材料位于铁电二维钙钛矿的下面，其中一个源漏电极与铁电二维钙钛矿相连接且另一个源漏电极与TMDs材料相连接。本发明提供了一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件及其制备方法，解决现有钙钛矿器件光电难以同时获取稳定性和高效光电探测性能这一技术难题。
Description
技术领域
本发明涉及光电转换器件和半导体物理器件技术领域，尤其涉及一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件。
背景技术
天空中的云层将近80％的辐射传递到了地球表面，这对人类产生了重大影响。目前，人们越来越关注光电转换技术在探测器中的应用，例如光通信、环境监测和化学、生物测试等方面。传统的光电探测器(PD)需要外部电池，这不仅增加了器件尺寸，而且使用寿命有限，维护成本可能非常昂贵。另一种技术上更合理的解决方案是使用可以独立运行的自供电PD，从而消除了对外部电源的需求。最近的研究进展表明，钙钛矿在光信号检测技术方面具有巨大的潜力，其性能与目前可用的硅和III-V族光电探测器相当。钙钛矿在光信号检测领域的发展得益于其优异的内在光电特性，例如接近100％的光致发光量子产率、大的扩散长度和可调谐的全波段吸收等。同时，动态有机成分提供了很大程度的分子运动自由度，这为材料的对称性破缺和电极化的提供了驱动力。二维杂化铁电体中的自供电光电探测行为很少被发现，二维钙钛矿铁电体(EA)2(MA)2Pb3Br10结合了优秀的半导体和光电特性表现出自供电光电探测行为。在钙钛矿器件中，垂直结构的探测器由于电子空穴阻挡层的引入，器件的暗电流和载流子迁移率很低。器件通常表现出低光电流低的响应度和快速响应时间。水平结构的器件通常表现出高光电流、高响应度和慢的响应时间。而高响应度和快速响应时间存在冲突，目前的探测器难以同时具备，从而导致高响应度和快速响应时间存在冲突。
发明内容
针对现有技术中所存在的不足，本发明提供了一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件，解决现有钙钛矿器件光电难以同时获取稳定性和高效光电探测性能这一技术难题。
本发明的上述技术目的是通过以下技术方案得以实现的：
一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件，包括支撑衬底、铁电二维钙钛矿、TMDs材料和两个源漏电极，所述铁电二维钙钛矿和TMDs材料铺设于支撑衬底上，所述铁电二维钙钛矿和TMDs材料相互重叠部分位于支撑衬底中部且TMDs材料位于铁电二维钙钛矿的下面，其中一个源漏电极与铁电二维钙钛矿相连接且另一个源漏电极与TMDs材料相连接。
本发明进一步设置为：支撑衬底选用刚性或柔性衬底材料，包括Si、Al2O3、PET中的任意一种；铁电二维钙钛矿为铁电二维钙钛矿材料，厚度为少层或者单层，结构为单晶或者多晶；TMDs材料为过渡金属硫化物材料，厚度为少层或者单层，源漏电极选用Ti、Cr、Au、Pd金属电极中的一种或选用石墨烯二维材料。
本发明还提供了铁电二维钙钛矿/二硫化钼垂直结构异质结器件的制备方法，包括以下步骤：
S1，将PDMS置于由透明玻璃片上，得到用于干法转移的PDMS转移垫片；
S2，用机械剥离法对铁电二维钙钛矿晶体材料进行剥离；
S3，采用机械剥离法对MoS2晶体材料进行反复剥离，在目标衬底上获得到多层或少层的MoS2二维材料；
S4，继续将步骤S2得到的铁电二维钙钛矿二维材料在室温下用干法转移技术转移至多层或少层的TMDs材料上，得到铁电二维钙钛矿/二硫化钼异质结器件；
S5，铁电二维钙钛矿/二硫化钼异质结器件两端上利用金属掩模版法制备出金属源漏电极。
本发明进一步设置为：在步骤S2中，将薄层铁电二维钙钛矿材料放在透明胶带上，然后将透明胶带反复对撕，将薄层材料撕至少层，再将对撕后的胶带粘在PDMS上，在PDMS上获得到多层或少层的铁电二维钙钛矿二维材料。
本发明进一步设置为：在步骤S4中，在光学显微镜下将PDMS转移垫片与TMDs材料对准，下降PDMS转移垫片使它和MoS2接触，1分钟到2分钟后缓慢将PDMS转移垫片抬起，得到铁电二维钙钛矿/二硫化钼垂直异质结。
本发明进一步设置为：在步骤S5中，将金属掩模版固定在硅片上，使电极位于异质结两端，随后用热蒸镀法蒸镀金电极。
本发明具有以下优点：
1、本发明提出一种以(EA)2(MA)2Pb3Br10(EA:乙胺离子，MA：甲胺离子)铁电二维钙钛矿材料与二维过渡金属硫化物(TMDs)材料二硫化钼异质结结构的光电探测器件，实现稳定性的高响应度低暗电流、高探测率、快速响应时间兼具的光电探测器件。利用铁电半导体的自发极化外部电场可调控的特点，精确调节极化电荷密度大小，从而实现探测器在无外加电压下探测到光电流。
2、本文发明的铁电二维钙钛矿/二硫化钼垂直结构异质结器件解决了垂直结构或者水平结构钙钛矿器件中高响应度与快速响应时间存在冲突的问题，从而有效的提高了钙钛矿光电探测器的光电性能，暗电流低至2.82×10-14A，响应度为0.1AW-1，上升时间和下降时间分别为1.3ms和3.01ms，比探测率为1.1×1012Jones，线性响应范围为45.8dB,同时器件的开关比可达到104。
3、利用(EA)2(MA)2Pb3Br10面内铁电极化特点，用外加电压调控材料内部极化强度，实现无外加电压下的光电探测，为下一代新型的无外部电路的自供电光电探测器提供了思路。
4、本发明提供的光电探测器的制备方法简单，操作方便，并且可扩展至其他二维钙钛矿材料上。
附图说明
图1为(EA)2(MA)2Pb3Br10/MoS2垂直异质结光电探测器件的结构示意图；
图2为(EA)2(MA)2Pb3Br10/MoS2垂直异质结光电探测器件暗态和不同光强下输出特性曲线，其中功率取值在暗态到6.78mW/cm2范围内递增；
图3为(EA)2(MA)2Pb3Br10/MoS2垂直异质结光电探测器件响应度随光强变化曲线；
图4为(EA)2(MA)2Pb3Br10/MoS2垂直异质结光电探测器件比探测率随光强变化曲线；
图5为(EA)2(MA)2Pb3Br10/MoS2垂直异质结光电探测器件的上升时间；
图6为(EA)2(MA)2Pb3Br10/MoS2垂直异质结光电探测器件的上下降时间；
图7为器件在不同极化电压下的输出特性曲线。
上述附图中：1、铁电二维钙钛矿；2、TMDs材料；3、源漏电极；4、支撑衬底。
具体实施方式
下面结合附图及实施例对本发明中的技术方案进一步说明。
一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件，包括支撑衬底4、铁电二维钙钛矿1、TMDs材料2和两个源漏电极3，所述铁电二维钙钛矿1和TMDs材料2铺设于支撑衬底4上，所述铁电二维钙钛矿1和TMDs材料2相互重叠部分位于支撑衬底4中部且TMDs材料2位于铁电二维钙钛矿1的下面，其中一个源漏电极3与铁电二维钙钛矿1相连接且另一个源漏电极3与TMDs材料2相连接。支撑衬底4选用Si，Al2O3，PET中的任意一种；铁电二维钙钛矿1为铁电二维钙钛矿材料，厚度为少层或者单层，结构为单晶或者多晶；TMDs材料2为过渡金属硫化物材料，厚度为少层或者单层，源漏电极选用Ti、Cr、Au、Pd金属电极中的一种或选用石墨烯二维材料。
一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件的制备方法，以(EA)2(MA)2Pb3Br10为例，包括以下步骤：
PDMS干法转移膜的制备。将固化剂和液体PDMS混合后搅拌半小时，随后用机械泵抽出溶液中的气泡。然后将溶液铺满平底培养皿中，随后将培养皿置于温度为70℃的烘箱中烘3h，得到具有一定厚度的PDMS固体膜；然后刀片划取大小约为5mm×5mm的PDMS膜，平整面朝上地放置于透明玻璃片一端，最后获得PDMS干法转移片。
样品的制备。首先采用机械剥离法从(EA)2(MA)2Pb3Br10晶体材料中获得少层的样品材料，并置于PDMS衬底上。还是机械剥离法从MoS2晶体材料中获得少层的样品材料，并置于含重掺杂Si的SiO2衬底上。
钙钛矿的干法转移。在显微镜和三微位移平台辅助下，显微镜辅助下对准PDMS转移片上的(EA)2(MA)2Pb3Br10和MoS2样品，然后缓慢均匀地压下。待PDMS片与SiO2衬底完全接触，2min后，再缓慢均匀地提起玻璃片，(EA)2(MA)2Pb3Br10落于SiO2衬底，得到(EA)2(MA)2Pb3Br10和MoS2垂直异质结构。
金属引出电极的制备。在显微镜和三维位移平台的辅助下将金属掩模版对准异质结的两端；再利用热蒸发镀膜设备以
的速率沉积制备出Au(50nm)的金属薄膜；完成器件的制备。
本发明利用二维钙钛矿铁电体(EA)2(MA)2Pb3Br10内部翻转对称性破缺引起的极化，通过源漏极两端输入电压调控材料自发极化强度大小，实现在无外加电压下的自供电光探测。采用PDMS常温干法转移有效避免温度对(EA)2(MA)2Pb3Br10的影响，极大地保持住样品材料的铁电性。
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。
Claims (6)
1.一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件，其特征在于：包括支撑衬底(4)、铁电二维钙钛矿(1)、TMDs材料(2)和两个源漏电极(3)，所述铁电二维钙钛矿(1)和TMDs材料(2)铺设于支撑衬底(4)上且部分重叠，所述铁电二维钙钛矿(1)和TMDs材料(2)相互重叠部分位于支撑衬底(4)中部且TMDs材料(2)位于铁电二维钙钛矿(1)的下方，其中一个源漏电极(3)与铁电二维钙钛矿(1)相连接且另一个源漏电极(3)与TMDs材料(2)相连接。
2.如权利要求1所述的一种基于铁电二维钙钛矿/二硫化钼垂直结构异质结器件，其特征在于：支撑衬底(4)选用Si、Al2O3、PET中的任意一种；源漏电极(3)选用Ti、Cr、Au、Pd金属电极中的任意一种或选用石墨烯二维材料。
3.如权利要求1或2所述的铁电二维钙钛矿/二硫化钼垂直结构异质结器件的制备方法，其特征在于，包括以下步骤：
S1，将PDMS置于透明玻璃片上，得到用于干法转移的PDMS转移垫片；
S2，用机械剥离法对铁电二维钙钛矿晶体材料进行剥离；
S3，采用机械剥离法对MoS2晶体材料进行反复剥离，在目标衬底上获得到多层或少层的MoS2二维材料；
S4，继续将步骤S2得到的铁电二维钙钛矿二维材料在室温下用PDMS干法转移技术转移至多层或少层的TMDs材料上，得到铁电二维钙钛矿/二硫化钼异质结器件；
S5，铁电二维钙钛矿/二硫化钼异质结器件两端上利用金属掩模版法制备出金属源漏电极。
4.如权利要求3所述的铁电二维钙钛矿/二硫化钼垂直结构异质结器件的制备方法，其特征在于：在步骤S2中，将薄层铁电二维钙钛矿材料放在透明胶带上，然后将透明胶带反复对撕，再将对撕后的胶带粘在PDMS转移垫片上，在PDMS转移垫片上获得到铁电二维钙钛矿二维材料。
5.如权利要求3所述的铁电二维钙钛矿/二硫化钼垂直结构异质结器件的制备方法，其特征在于：在步骤S4中，在光学显微镜下将PDMS转移垫片与TMDs材料对准，下降PDMS转移垫片使它和MoS2接触，1分钟到2分钟后缓慢将PDMS转移垫片抬起，得到铁电二维钙钛矿/二硫化钼垂直异质结。
6.如权利要求3所述的铁电二维钙钛矿/二硫化钼垂直结构异质结器件的制备方法，其特征在于：在步骤S5中，将金属掩模版固定在硅片上，使电极位于异质结两端，随后用热蒸镀法蒸镀金电极。
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