CN110491966A - 碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器及其制作方法 - Google Patents
碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器及其制作方法 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 25
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- 238000000034 method Methods 0.000 claims description 12
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- 238000004519 manufacturing process Methods 0.000 claims description 4
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Abstract
本发明公开了碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器及其制作方法，是在绝缘基底上生长有PtTe2薄膜，在PtTe2薄膜上的局部区域生长有MAPbBr3钙钛矿单晶，PtTe2薄膜与MAPbBr3钙钛矿单晶形成异质结。本发明的光电探测器，制备过程简单、性能稳定、性能好，为过渡族金属碲化物及钙钛矿材料在光电探测器中的应用开拓了新的前景。
Description
技术领域
本发明属于半导体光电探测器领域，具体涉及一种PtTe2/MAPbBr3钙钛矿单晶异质结光电探测器及其制作方法。
背景技术
有机/无机卤化物钙钛矿材料在过去十年中因其优异的光电性能而受到广泛的研究兴趣，包括长扩散长度、低捕获密度、大吸收系数和多波段光吸收。因具有这些独特的性质，这一组混合卤化物材料作为组装各种光电器件的构件具有很大的潜力，包括发光二极管(LED)、激光器、太阳能电池和光电探测器等。在这些光电子器件中，光电探测器对于它们在基础科学和工业领域的有前景的应用非常重要，例如成像传感、光通信、夜视和环境监测等。利用钙钛矿薄膜可以制备高性能宽波段的光电探测器，其薄膜的制备可通过简单旋涂获得，但其较差的稳定性制约了其进一步应用，通常研究者们通过表面修饰或表面覆膜的方式来提高其稳定性，但同时亦提高了制备成本并且抑制了钙钛矿材料本身的光电性能，因此开始逐渐转向钙钛矿单晶的合成及其光电性能的研究。钙钛矿单晶不仅拥有优异光电性能，而且由于单晶具备较低的缺陷态以及较高的结晶度，使其具备相对较高的稳定性。
二维(2D)层状过渡金属二硫化物(TMD)材料由于独特的厚度依赖性、高载流子迁移率和良好的空气稳定性，而在电子和光电子应用中显示出巨大的潜力。由于这些出色的性能，2D层状TMD(例如MoS2、WS2和PdSe2)已成功与钙钛矿薄膜结合来制作光电探测器，包括光电导体、光电晶体管和光电二极管。这些检测器虽表现出增强的光电导增益和光响应特性，但其性能仍有待进一步提高。相较于传统的TMD半导体材料，PtTe2具有更加优异的导电性能，或可以大幅提高器件载流子传输能力，从而提高器件性能。但是作为特殊的半金属材料，PtTe2能否与钙钛矿材料结合、与何种钙钛矿材料可以结合以及如何结合可以获得高性能的器件，具有重要的研究价值。
发明内容
本发明的目的在于构建碲化铂/甲基氨铅溴钙钛矿单晶异质结制光电探测器，以期可以利用钙钛矿单晶较高的吸光度、高载流子浓度以及较高的稳定性，和碲化铂较高的导电性能及较高的温度性，来制备具有较高稳定性的高性能光电探测器。
本发明解决技术问题，采用如下技术方案：
碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器，其特点在于：是在绝缘基底上生长有PtTe2薄膜，在所述PtTe2薄膜上的局部区域生长有MAPbBr3钙钛矿单晶，所述PtTe2薄膜与所述MAPbBr3钙钛矿单晶形成异质结；在所述绝缘基底还设置有两金属电极，其中一金属电极位于MAPbBr3钙钛矿单晶上，另一金属电极位于未生长MAPbBr3钙钛矿单晶的PtTe2薄膜上。
进一步地，所述PtTe2薄膜的厚度在20-40nm之间。更进一步地，所述PtTe2薄膜是先在绝缘基底上通过电子束蒸发法蒸镀一层5-10nm厚的铂薄膜，再用热辅助转化法，在碲氛围中将铂转化为碲化铂，从而获得PtTe2薄膜。
进一步地，所述MAPbBr3钙钛矿单晶厚度在0.5-3mm之间。更进一步地，所述MAPbBr3钙钛矿单晶是通过溶液法在PtTe2薄膜上生长获得。
进一步地，所述金属电极为Au电极、Ti电极或Ag电极，所述金属电极的厚度为50nm-200nm。
本发明所述碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器的制作方法，包括如下步骤：
A、将绝缘基底依次用丙酮、酒精、去离子水超声清洗后，吹干备用；
B、在绝缘基底上通过电子束蒸镀法，在真空度6.7×10-3Pa以下，蒸镀一层5-10nm厚的铂薄膜；
C、将表面覆盖有铂薄膜的绝缘基底放入双温区管式炉的右温区，将盛有0.1g纯度为99.99％的碲粉的瓷舟放入双温区管式炉的左温区；通入流量为50sccm的氩氢混合气为保护气体，将左温区升温至250℃，将右温区升温至500-560℃，保持管式炉内压强为20Pa；维持反应条件1h之后，关闭双温区管式炉的加热系统，继续通入流量为50sccm的氩氢混合气，等待双温区管式炉冷却至室温时取出绝缘基底，即在绝缘基底表面生长有厚度在20-40nm之间的PtTe2薄膜；
D、将PtTe2薄膜上不需生长MAPbBr3钙钛矿单晶的区域覆盖；
将MABr和PbBr2按摩尔比1：1溶于DMF溶液中，获得二者摩尔浓度皆为0.5mol/L的前驱体溶液；然后将覆盖后的绝缘基底水平浸放在所述前驱体溶液中，80℃下保温6-12h，即在未覆盖区域生长出0.5-3mm厚的MAPbBr3钙钛矿单晶；
E、将不需蒸镀金属电极的区域覆盖，然后通过电子束蒸发法在绝缘基底上蒸镀两金属电极，其中一金属电极位于MAPbBr3钙钛矿单晶上，另一金属电极位于未生长MAPbBr3钙钛矿单晶的PtTe2薄膜上，即完成光电探测器的制备。
与已有技术相比，本发明的有益效果体现在：
1、本发明基于PtTe2薄膜和MAPbBr3钙钛矿单晶的异质结光电探测器，器件制备过程简单、性能稳定、性能良好，为过渡族金属碲化物和钙钛矿单晶材料在光电探测器中的应用开拓了新的前景。
2、本发明选用PtTe2，其具有较高的稳定性和优异的导电性能，从而提高了器件的光电性能。
3、本发明的光电探测器，MAPbBr3钙钛矿单晶在紫外可见光范围内具有较高吸收系数、较高的载流子浓度以及较高的稳定性，与PtTe2协同，因此制备的器件性能好，稳定性高。
4、本发明中的PtTe2薄膜和MAPbBr3钙钛矿单晶异质结光电探测器可以工作于零电压下，无需消耗外部能量，因而可有效降低功耗。
附图说明
图1为PtTe2/MAPbBr3钙钛矿单晶异质结制光电探测器的结构示意图，其中：1为PtTe2薄膜，2为MAPbBr3钙钛矿单晶，3为金属电极，4为绝缘基底。
图2为本发明实施例1中所得光电探测器在黑暗条件下的电流-电压特性曲线。
图3为本发明实施例1中所得光电探测器在黑暗条件下和520nm波长(11.5mW/cm2)光照下的电流-电压特性曲线。
图4为本发明实施例1中所得光电探测器在零工作电压下，在520nm波长(11.5mW/cm2)光照下的时间电流响应。
图5为本发明实施例1中所得光电探测器在5伏工作电压下，在520nm波长(11.5mW/cm2)光照下的时间电流响应。
具体实施方式
下面结合附图对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
如图1所示，PtTe2/MAPbBr3钙钛矿单晶异质结光电探测器，是在绝缘基底4上生长有PtTe2薄膜1，在PtTe2薄膜1上的局部区域生长有MAPbBr3钙钛矿单晶2，PtTe2薄膜1与MAPbBr3钙钛矿单晶2形成异质结；在绝缘基底4还设置有两金属电极3，其中一金属电极位于MAPbBr3钙钛矿单晶上，另一金属电极位于未生长MAPbBr3钙钛矿单晶的PtTe2薄膜上。
进一步地，本实施例中所用绝缘基底为氧化硅片，所用金属电极为50nm金电极。
本实施例光电探测器的制作方法，包括如下步骤：
A、将氧化硅片依次用丙酮、酒精、去离子水超声清洗后，吹干备用。
B、在氧化硅片上通过电子束蒸镀法，在真空度6.7×10-3Pa以下，蒸镀一层8nm厚的铂薄膜；
C、将表面覆盖有铂薄膜的氧化硅片放入双温区管式炉的右温区，将盛有0.1g纯度为99.99％的碲粉的瓷舟放入双温区管式炉的左温区；通入流量为50sccm的氩氢混合气(氢气体积百分比占5％)为保护气体，将左温区升温至250℃，将右温区升温至550℃，保持管式炉内压强为20Pa；维持反应条件1h之后，关闭双温区管式炉的加热系统，继续通入流量为50sccm的氩氢混合气，等待双温区管式炉冷却至室温时取出绝缘基底，即在绝缘基底表面生长有厚度在32-35nm之间的PtTe2薄膜；
D、将PtTe2薄膜上不需生长MAPbBr3钙钛矿单晶的区域粘上胶带覆盖；
将MABr和PbBr2按摩尔比1：1溶于DMF溶液中，获得二者摩尔浓度皆为0.5mol/L的前驱体溶液；然后将覆盖后的氧化硅片水平浸放在所述前驱体溶液中，80℃下保温6h，即在未覆盖区域生长出2-3mm厚的MAPbBr3钙钛矿单晶；
E、将不需蒸镀金属电极的区域用铜箔覆盖，然后通过电子束蒸发法在绝缘基底上蒸镀两50nm的金电极，其中一金电极位于MAPbBr3钙钛矿单晶上，另一金电极位于未生长MAPbBr3钙钛矿单晶的PtTe2薄膜上，即完成PtTe2/MAPbBr3钙钛矿单晶异质结光电探测器的制备。
本实施例所制备的PtTe2/MAPbBr3钙钛矿单晶异质结光电探测器在黑暗下的电流-电压特性曲线如图2所示，从图中可以看出探测器具有明显的整流特性，整流比约等于10。
本实施例所制备的PtTe2/MAPbBr3钙钛矿单晶异质结光电探测器在黑暗下和波长为520nm、强度为11.5mW/cm2的光照下的电流-电压特性曲线如图3所示，从图中可以看出探测器在正向偏压下具有明显的光电响应特性。
本实施例所制备的PtTe2/MAPbBr3钙钛矿单晶异质结光电探测器在零工作电压下，在波长为520nm、强度为11.5mW/cm2的光照下的时间响应曲线如图4所示，从图中可以看出探测器对被探测光非常敏感，且具有超快的响应速度。此外制备的PtTe2/MAPbBr3钙钛矿单晶异质结光电探测器在零工作电压下可以正常工作，可有效降低器件功耗。
本实施例所制备的PtTe2/MAPbBr3单晶异质结光电探测器在5V工作电压下，在波长为520nm、强度为11.5mW/cm2的光照下的时间响应曲线如图5所示，从图中可以看出探测器具有较快的响应速度，电流开关比约为15，且在正向偏压下有明显的光响应。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器，其特征在于：是在绝缘基底上生长有PtTe2薄膜，在所述PtTe2薄膜上的局部区域生长有MAPbBr3钙钛矿单晶，所述PtTe2薄膜与所述MAPbBr3钙钛矿单晶形成异质结；在所述绝缘基底还设置有两金属电极，其中一金属电极位于MAPbBr3钙钛矿单晶上，另一金属电极位于未生长MAPbBr3钙钛矿单晶的PtTe2薄膜上。
2.根据权利要求1所述的碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器，其特征在于：所述PtTe2薄膜的厚度在20-40nm之间。
3.根据权利要求1或2所述的碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器，其特征在于：所述PtTe2薄膜是先在绝缘基底上通过电子束蒸发法蒸镀一层5-10nm厚的铂薄膜，再用热辅助转化法，在碲氛围中将铂转化为碲化铂，从而获得PtTe2薄膜。
4.根据权利要求1所述的碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器，其特征在于：所述MAPbBr3钙钛矿单晶厚度在0.5-3mm之间。
5.根据权利要求1所述的碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器，其特征在于：所述MAPbBr3钙钛矿单晶是通过溶液法在PtTe2薄膜上生长获得。
6.根据权利要求1所述的碲化铂/甲基氨铅溴钙钛矿单晶异质结光电探测器，其特征在于：所述金属电极为Au电极、Ti电极或Ag电极，所述金属电极的厚度为50nm-200nm。
7.一种权利要求1～5中任意一项所述光电探测器的制作方法，其特征在于，包括如下步骤：
A、将绝缘基底依次用丙酮、酒精、去离子水超声清洗后，吹干备用；
B、在绝缘基底上通过电子束蒸镀法，在真空度6.7×10-3Pa以下，蒸镀一层5-10nm厚的铂薄膜；
C、将表面覆盖有铂薄膜的绝缘基底放入双温区管式炉的右温区，将盛有0.1g纯度为99.99％的碲粉的瓷舟放入双温区管式炉的左温区；通入流量为50sccm的氩氢混合气为保护气体，将左温区升温至250℃，将右温区升温至500-560℃，保持管式炉内压强为20Pa；维持反应条件1h之后，关闭双温区管式炉的加热系统，继续通入流量为50sccm的氩氢混合气，等待双温区管式炉冷却至室温时取出绝缘基底，即在绝缘基底表面生长有厚度在20-40nm之间的PtTe2薄膜；
D、将PtTe2薄膜上不需生长MAPbBr3钙钛矿单晶的区域覆盖；
将MABr和PbBr2按摩尔比1：1溶于DMF溶液中，获得二者摩尔浓度皆为0.5mol/L的前驱体溶液；然后将覆盖后的绝缘基底水平浸放在所述前驱体溶液中，80℃下保温6-12h，即在未覆盖区域生长出0.5-3mm厚的MAPbBr3钙钛矿单晶；
E、将不需蒸镀金属电极的区域覆盖，然后通过电子束蒸发法在绝缘基底上蒸镀两金属电极，其中一金属电极位于MAPbBr3钙钛矿单晶上，另一金属电极位于未生长MAPbBr3钙钛矿单晶的PtTe2薄膜上，即完成光电探测器的制备。
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