CN108649082A - 一种ZnS碳量子点日盲紫外探测器及其制备方法 - Google Patents
一种ZnS碳量子点日盲紫外探测器及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种ZnS碳量子点日盲紫外探测器及其制备方法，所述日盲紫外探测器包括ZnS量子点‑碳量子点混合层。其制备方法是先分别制备ZnS量子点溶液和碳量子点溶液，然后将其按一定比例混合后通过印刷、滴涂或旋涂的方式在印有金属电极的基底上制成ZnS量子点‑碳量子点混合层。本发明解决了基于ZnS量子点的日盲紫外探测器中，由于ZnS量子点载流子迁移率低而导致器件光电流、响应度和探测度偏低的问题，提供了一种ZnS碳量子点日盲紫外探测器及其制备方法，利用碳量子点作为载流子传输层，可以极大程度的提高探测器的光响应电流，从而提高响应度，达到提高器件性能的目的。
Description
技术领域
本发明属于光电子器件技术领域，具体涉及一种ZnS碳量子点日盲紫外探测器及其制备方法。
背景技术
太阳辐射中的一部分紫外光，在通过大气层过程中受到热层氧原子和平流层臭氧层的强烈吸收，使得短于300 nm波长的紫外光几乎达不到地球近地表空间。这样在近地表面太阳辐射中300 nm以下部分基本形成盲区，这个波段被称为“日盲紫外区”。针对日盲区的紫外光电探测器，背景噪声很小，几乎不受太阳辐射的干扰。所以日盲紫外探测技术是一项在民用和军用都非常有应用价值的探测技术，尤其在火焰与弧光探测、环境监测、生化基因检测、空间通信、飞行器制导等诸多方面。随着新型半导体材料的发展，基于宽禁带半导体（如AlGaN、SiC 、SiZnO、MgZnO、Ga2O3、金刚石等）的日盲紫外探测器已经得到较为深入的研究，部分实现了产业化。但是也存在一些问题，比如随着Al组分的增加，高质量高空穴浓度的p型AlGaN外延薄膜的制备就比较困难；类似的，高Mg组分的MgZnO较难生长出单晶纤锌矿结构。虽然这些困难目前也在逐步解决，不过一定程度上制约了这些宽禁带半导体材料在日盲紫外探测领域的发展。此外，由于此类传统半导体器件加工工艺较为复杂、制备成本高昂，在大面积生产和柔性应用方面有限制。
硫化锌（ZnS）是一种宽禁带半导体材料，其室温下的体材料的禁带宽度约为3.6eV（立方闪锌矿结构）和3.8 eV（六方纤锌矿结构），激子束缚能约为40 meV。然而ZnS量子点的载流子迁移率较低，制备成探测器件后，虽然暗电流极小，但是光响应电流微弱，不利于信号识别。在混入碳量子点后，ZnS量子点的光生电子可以迅速转移到碳量子点中，加速分离电子和空穴，可以极大程度的提高探测器的光响应电流。结合印刷电子工艺，可以基于CMOS集成电路制备日盲紫外光电晶体管阵列，促进产业升级及多样化应用。
发明内容
本发明解决了基于ZnS量子点的日盲紫外探测器中，由于ZnS量子点载流子迁移率低而导致器件光电流、响应度和探测度偏低的问题，提供了一种ZnS碳量子点日盲紫外探测器及其制备方法，利用碳量子点作为载流子传输层，可以极大程度的提高探测器的光响应电流，从而提高响应度，达到提高器件性能的目的。
一种ZnS碳量子点日盲紫外探测器，包括ZnS量子点-碳量子点混合层。
上述ZnS碳量子点日盲紫外探测器的制备方法，包括以下步骤：
步骤1，采用化学溶液法合成ZnS量子点，将其分散在乙醇中制成ZnS量子点溶液待用；
步骤2，采用化学溶液法合成碳量子点，将其分散在甲苯中制成碳量子点溶液待用；
步骤3，在基底上制备金属电极；
步骤4，将ZnS量子点溶液和碳量子点溶液混合，混合液通过印刷、滴涂或旋涂的方式在步骤3的基底上制成ZnS量子点-碳量子点混合层，烘干，即得。
进一步地，步骤1中ZnS量子点的直径在2 nm。
进一步地，步骤1中ZnS量子点溶液中ZnS量子点的浓度为0.2 mol/L。
进一步地，步骤2中碳量子点的直径在2-6 nm。
进一步地，步骤2中碳量子点溶液中碳量子点的浓度为0.8 mol/L。
进一步地，步骤4所述混合液中ZnS量子点和碳量子点的摩尔比为10:1-1:1。
进一步地，步骤4中ZnS量子点-碳量子点混合层的膜厚在0.2-2 μm，烘干条件为120℃、1h。
ZnS量子点的载流子迁移率较低，制备成探测器件后，虽然暗电流极小，但是光响应电流微弱，不利于信号识别。很多半导体光电探测器，为了尽快把电子和空穴收集到电极，金属电极的距离要求非常近，这样在工艺上存在一定的难度。而碳/石墨烯量子点，有较高的电子迁移率和导热性，并且材料结构稳定，可以快速转移电子，对金属电极没有很近的距离要求。碳量子点可以减少界面阻抗，加速ZnS量子点中光生电子-空穴对的分离和漂移。基于ZnS量子点的日盲紫外探测器中，由于ZnS量子点载流子迁移率低而导致器件光电流、响应度和探测度偏低的问题，提出并ZnS量子点-碳量子点混合层作为光敏层的光电探测器，利用碳量子点作为载流子传输层，可以极大程度的提高探测器的光响应电流，从而提高响应度，达到提高器件性能的目的。
与现有技术相比，本发明的日盲紫外探测器，完全基于溶液过程的制备工艺，适用于印刷电子工艺制备，可以实现低成本、大面积生产。
附图说明
图1为实施例1制备的MSM日盲紫外探测器结构示意图，101为基底，102为金属电极，103为ZnS-碳量子点混合薄膜。
图2是实施例1制备的MSM日盲紫外探测器的剖面结构示意图，101为基底，102为金属电极，103为ZnS-碳量子点混合薄膜。
图3是实施例2制备的硅基日盲紫外探测器的剖面结构示意图。
图4是实施例3制备的柔性日盲紫外探测器的剖面结构示意图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步详细描述。
本发明中实施例所采用的ZnS量子点和碳量子点通过以下方法制备得到。
ZnS量子点的具体制备过程：在空气环境中，采用化学溶液法，二水乙酸锌作为锌源，硫代乙酰胺缓慢水解生成硫化氢，通过置换反应，得到ZnS。步骤如下：把10 mmol (2.20g) 二水乙酸锌溶解在70 ℃的100 mL乙醇中；在冰浴条件下，把10 mmol (0.75 g) 硫代乙酰胺溶于50 mL的0 ℃乙醇。将上述两种溶液混合，在60 ℃下强力搅拌20分钟，加入3倍体积比的正庚烷，以大于5000 xg离心力析出。再次加入正庚烷/乙醇混合溶液清洗，超声分散后再次离心，干燥后以浓度0.2 mol/L (19 mg/mL) 重新分散在乙醇中保存。
碳量子点的具体制备过程。十八烯作为非配位性溶剂, 十六胺作为表面钝化剂，无水柠檬酸作为碳源。简要步骤如下： 在氩气保护下，把1.5 g十六胺溶解在300 ℃的15mL十八烯中，然后把5 mmol (0.96 g) 无水柠檬酸加入上述溶液。保持一定时间，用丙酮多次清洗后，得到约0.1 g (8 mmol) 碳量子点产物，以浓度0.8 mol/L (~10 mg/mL) 分散在甲苯中保存。
实施例1
如图1、图2所示的金属-半导体-金属（MSM）肖特基结日盲紫外探测器，其制备方法包括如下步骤：
步骤1，将玻璃基片或者PET基底101，依次在去离子水、丙酮、异丙醇中超声15分钟，放置于烘箱中在110℃条件下烘干。
步骤2，通过热蒸发或磁控溅射方法，使用掩膜制备金属电极图案102，膜厚约100nm，电极间距5-20 μm。
步骤3，取8 mL浓度0.2 mol/L 的ZnS量子点溶液，混合1 mL浓度0.8 mol/L碳量子点溶液，通过滴涂或旋涂的方式制备在基底101上。随即在120℃烘干1小时，得到ZnS-碳量子点混合薄膜103，膜厚约0.2-1 μm。
至此完成ZnS-碳量子点MSM日盲紫外探测器的基本制备。制得的ZnS-碳量子点日盲紫外探测器在200-290 nm波段具有较高的光响应电流。
实施例2
如图3所示的硅基日盲紫外光电晶体管，其制备方法包括如下步骤：
步骤1，将氧化硅片（包括n掺杂Si作为栅极201，氧化硅介电层202），依次在去离子水、丙酮、异丙醇中超声15分钟，放置于烘箱中在120℃条件下烘干。
步骤2，取ZnS量子点和碳量子点混合溶液，通过微电子打印机（材料喷印沉积仪）喷墨打印的方式制备在氧化硅介电层202上。随即在120℃烘干1小时，得到ZnS-碳量子点混合薄膜203。
步骤3，把银纳米颗粒按照一定的图案，喷墨打印在ZnS-碳量子点混合薄膜203上，随即于150℃退火2分钟，形成源漏电极204。
至此完成ZnS-碳量子点硅基日盲光电晶体管的基本制备。
实施例3
如图4所示的柔性日盲紫外光电晶体管，其制备方法包括如下步骤：
步骤1，将柔性PET基底301，依次在去离子水、丙酮、异丙醇中超声15分钟，放置于烘箱中在110℃条件下烘干。
步骤2，用微电子打印机（材料喷印沉积仪）把银纳米颗粒喷墨打印在基底301上，随即于150℃退火2分钟，形成栅极302。
步骤4，把聚（4-乙烯苯酚）（PVP），喷墨打印在栅极302上，随即于100℃烘干30分钟，形成介电层303。
步骤4，取ZnS量子点和碳量子点混合溶液，通过喷墨打印的方式制备在介电层303之上。随即在120 ℃烘干1小时，得到ZnS-碳量子点混合薄膜304。
步骤5，把银纳米颗粒按照一定的图案，喷墨打印在ZnS-碳量子点混合薄膜304上，随即于150℃退火2分钟，形成源漏电极305。
至此完成ZnS-碳量子点柔性日盲光电晶体管的基本制备。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何形式上的限制，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，依据本发明的技术实质，对以上实施例所作的任何简单的修改、等同替换与改进等，均仍属于本发明技术方案的保护范围之内。
Claims (8)
1.一种ZnS碳量子点日盲紫外探测器，其特征在于：包括ZnS量子点-碳量子点混合层。
2.权利要求1所述的ZnS碳量子点日盲紫外探测器的制备方法，其特征在于：包括以下步骤：
步骤1，采用化学溶液法合成ZnS量子点，将其分散在乙醇中制成ZnS量子点溶液待用；
步骤2，采用化学溶液法合成碳量子点，将其分散在甲苯中制成碳量子点溶液待用；
步骤3，在基底上制备金属电极；
步骤4，将ZnS量子点溶液和碳量子点溶液混合，混合液通过印刷、滴涂或旋涂的方式在步骤3的基底上制成ZnS量子点-碳量子点混合层，烘干，即得。
3.根据权利要求2所述的ZnS碳量子点日盲紫外探测器的制备方法，其特征在于：步骤1中ZnS量子点的直径在2 nm。
4.根据权利要求2所述的ZnS碳量子点日盲紫外探测器的制备方法，其特征在于：步骤1中ZnS量子点溶液中ZnS量子点的浓度为0.2 mol/L。
5.根据权利要求2所述的ZnS碳量子点日盲紫外探测器的制备方法，其特征在于：步骤2中碳量子点的直径在2-6 nm。
6.根据权利要求2所述的ZnS碳量子点日盲紫外探测器的制备方法，其特征在于：步骤2中碳量子点溶液中碳量子点的浓度为0.8 mol/L。
7.根据权利要求2所述的ZnS碳量子点日盲紫外探测器的制备方法，其特征在于：步骤4所述混合液中ZnS量子点和碳量子点的摩尔比为10:1-1:1。
8.根据权利要求2所述的ZnS碳量子点日盲紫外探测器的制备方法，其特征在于：步骤4中ZnS量子点-碳量子点混合层的膜厚在0.2-2 μm，烘干条件为120℃、1h。
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