CN109524478B - 基于二硫化锡薄膜的柔性光电探测器件 - Google Patents
基于二硫化锡薄膜的柔性光电探测器件 Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及基于二硫化锡薄膜的柔性光电探测器件。本发明提供一种(001)晶面取向的二硫化锡薄膜，其为二硫化锡晶态薄膜，具有(001)晶面方向取向性。还提供一种基于二硫化锡薄膜的光电探测器件，包括权利要求1所述的二硫化锡薄膜，和平行设在二硫化锡薄膜上的两个电极。本发明的二硫化锡薄膜均匀性、致密性好，具有(001)晶面取向，有利于二硫化锡薄膜具有优良的柔性。本发明提供的二硫化锡光电探测器柔性好，可承受弯曲度高，且可承受大量弯曲次数，经过一万次以上弯曲性能基本保持不变。
Description
技术领域
本发明涉及半导体薄膜领域，尤其涉及一种(001)晶面取向的二硫化锡连续薄膜及基于该薄膜的光电探测器件。
背景技术
二硫化锡(SnS2)是一种稳定的硫族化合物半导体材料，其中锡和硫两种元素在地壳中的含量较高、且对环境友好。该材料电荷迁移率可以达到50cm2V-1s-1，具有较宽的光学禁带宽度2.8eV，在紫外光区具有较好的光电响应。更为重要的是二硫化锡具有与石墨烯、硫化钼、硫化钨等类似的二维层状结构，在光电子材料领域具有广泛的应用前景。
二硫化锡材料在(001)晶面方向的载流子传输机制与一般无机半导体材料不同，可以进行跳跃式传输，另外具有(001)晶面方向优势取向的二硫化锡层状结构趋势性更加一致，有利于二硫化锡薄膜的柔性。目前，制备二硫化锡材料的方法较多，如溶剂热法、热注入法、金属硫化法、化学浴沉积法等，但都难以实现制备具有(001)晶面优势取向的二硫化锡薄膜材料。2015年专利201510178074.9公开了一种在650℃～750℃条件下利用化学气相沉积的方法制备具有(001)晶面优势取向二硫化锡纳米晶体薄膜的方法，但该方法制备的二硫化锡薄膜有明显的不足：(1)温度条件过高，一般基底材料难以承受；(2)制备的薄膜是由颗粒组成的，不连续。以上问题导致该方法制备的二硫化锡薄膜不适合于宏观器件的制备应用。
综上所述，在较低温度下制备出具有(001)晶面优势取向的二硫化锡纳米晶体连续薄膜材料是急需解决的问题。该问题的解决也将进一步促进二硫化锡材料在柔性光电器件中的应用。
发明内容：
本发明所要解决的问题是：提供一种(001)晶面取向的二硫化锡、基于二硫化锡薄膜的光电探测器件以及大面积制备二硫化锡半导体薄膜材料的方法。
本发明对要解决的问题所采取的技术方案是：
一种(001)晶面取向的二硫化锡薄膜，其为晶态薄膜，具有(001)晶面方向取向性。
按上述方案，所述的二硫化锡薄膜包括基底。
按上述方案，所述的基底材料为聚酰亚胺塑料、玻璃、FTO等。
一种大面积制备上述二硫化锡半导体薄膜材料的方法，在基底材料表面蒸发沉积一层二硫化锡薄膜前驱体，在惰性气氛保护的条件下对薄膜进行250℃～400℃热处理，获得具有(001)晶面方向取向性的二硫化锡晶态薄膜。
按上述方案，所述惰性气氛保护的条件中，气氛为氮气、氩气等。
按上述方案，所述的热处理时间为30min以上，优选为30～300min。
基于二硫化锡薄膜的光电探测器件，包括前述二硫化锡薄膜，和平行设在二硫化锡薄膜上的两个电极。
按上述方案，所述的电极为金电极；两个电极间距为220微米。
按上述方案，所述的基底材料为聚酰亚胺塑料，由此构成柔性光电探测器件。该器件经过折叠后性能可基本维持原有性能水平；器件经过大于11000次小于10度弯曲后可基本维持原有性能水平。可承受弯曲度高，且可承受大量弯曲次数。
一种二硫化锡光电探测器的制备方法，其制备步骤依此如下：
(1)、利用蒸发的方法在经清洁处理过的基底材料表面蒸镀一层二硫化锡薄膜；
(2)、将上述样品放置到惰性气氛保护的条件下250℃～400℃热处理，自然冷却后取出；
(3)、在热处理过的样品上利用热蒸发的方法制备两个电极，构成平行式的光电导型。
按上述方案，步骤(3)所述的热蒸发为利用真空蒸镀技术在晶化后的二硫化锡薄膜表面蒸镀金电极形成光电探测器件。
本发明的优点：
(1)本发明的二硫化锡薄膜均匀性、致密性好，具有(001)晶面取向，有利于二硫化锡薄膜具有优良的柔性。
(2)本发明提供的二硫化锡薄膜采用热蒸发的方法并配合热处理制备，制备的薄膜均匀性、致密性好、连续性好；可以大面积制备，晶面取向可控，方法简便，由此可以实现大面积器件制备；
(3)利用本方法制备的二硫化锡薄膜晶体取向性好，为(001)晶面取向；
(4)本发明提供的二硫化锡光电探测器柔性好，可承受弯曲度高，且可承受大量弯曲次数，经过一万次以上弯曲性能基本保持不变。
附图说明
图1、实施例1制备的SnS2薄膜的XRD图谱。
图2、实施例2制备的SnS2薄膜的XRD图谱。
图3、实施例3制备的SnS2薄膜的XRD图谱。
图4、实施例4制备的SnS2薄膜的XRD图谱。
图5、实施例5制备的SnS2薄膜的XRD图谱。
图6-1、实施例6制备的SnS2薄膜柔性光电探测器件示意图。
图6-2、实施例6制备的SnS2薄膜柔性光电探测器件柔性性能测试曲线。
图7、实施例7制备的SnS2薄膜柔性光电探测器件柔性性能测试曲线。
具体实施方式
实施例1
1.将FTO基底材料在洗洁精中超声清洗30min，然后在氨水、双氧水和去离子水的混合溶剂中80℃处理30min，完成用去离子水超声10min，最后在烘箱中80℃干燥，待用。
2.称取150mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为250℃，处理时间为30min。完成后，自然冷却至室温。
3.利用X射线粉末衍射仪对制备的样品进行表征。图1为本实施例条件下制备样品的XRD图谱，在15.04度出现了SnS2的(001)晶面特征衍射峰。
实施例2
1.基底材料及处理同实施例1。
2.称取150mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为350℃，处理时间为30min。完成后，自然冷却至室温。
3.利用X射线粉末衍射仪对制备的样品进行表征。图2为本实施例条件下制备样品的XRD图谱，在15.04度出现了SnS2的(001)晶面特征衍射峰，相对强度较高，结晶较好。
实施例3
1.基底材料及处理同实施例1。
2.称取150mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为400℃，处理时间为30min。完成后，自然冷却至室温。
3.利用X射线粉末衍射仪对制备的样品进行表征。图3为本实施例条件下制备样品的XRD图谱，在15.04度出现了SnS2的(001)晶面特征衍射峰，相对强度较高，结晶较好。
实施例4
1.将聚酰亚胺塑料薄膜材料在异丙醇中超声清洗30min，然后在烘箱中80℃干燥，待用。
2.称取150mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为350℃，处理时间为120min。完成后，自然冷却至室温。
3.利用X射线粉末衍射仪对制备的样品进行表征。图4为本实施例条件下制备样品的XRD图谱，在15.04度出现了SnS2的(001)晶面特征衍射峰，相对强度较高，结晶较好，其余衍射峰来自基底材料聚酰亚胺。
实施例5
1.将聚酰亚胺塑料薄膜材料在异丙醇中超声清洗30min，然后在烘箱中80℃干燥，待用。
2.称取300mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为350℃，处理时间为300min。完成后，自然冷却至室温。
3.利用X射线粉末衍射仪对制备的样品进行表征。图5为本实施例条件下制备样品的XRD图谱，在15.04度出现了SnS2的(001)晶面特征衍射峰，相对强度较高，结晶较好，其余衍射峰来自基底材料聚酰亚胺。
实施例6
1.SnS2薄膜制备过程如实施例5。
2.在上述薄膜表面蒸镀金电极完成器件组装，电极之间的间距为220μm。器件示意图见图6-1，其中D1为聚酰亚胺基底，D2为SnS2薄膜，D3为金电极。
3.将上述器件连接到电化学工作中(CHI 660E)上进行IV曲线测试，光源为405nm点状激光，光源强度为10μJ，测试曲线见图6-2a曲线。将上述器件反复弯曲11000次(弯曲角度小于10度)后测试IV曲线，光源为405nm点状激光，光源强度为10μJ，测试曲线见图6-2b曲线。两条曲线对比显示器件性能基本保持，说明本方法制备的SnS2薄膜及器件具有优异的柔性。与现有报道的二硫化锡比较，本方法制备的探测器显示出更佳的光电响应度。
实施例7
1.SnS2薄膜制备过程如实施例4。
2.器件结构同实施例6。
3.将上述器件连接到电化学工作中(CHI 660E)上进行IV曲线测试，光源为405nm点状激光，光源强度为10μJ，测试曲线见图7a曲线。将上述器件折叠(对折，有折痕)，后测试IV曲线，光源为405nm点状激光，光源强度为10μJ，测试曲线见图7b曲线。两条曲线对比显示器件性能基本保持，说明本方法制备的SnS2薄膜及器件具有优异的柔性。
对比例1
1.基底材料及处理同实施例1。
2.称取150mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为150℃，处理时间为30min。完成后，自然冷却至室温。
3.利用X射线粉末衍射仪对制备的样品进行表征，未检测到衍射峰，表明材料未结晶。
对比例2
1.基底材料及处理同实施例1。
2.称取300mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为200℃，处理时间为30min。完成后，自然冷却至室温。
3.利用X射线粉末衍射仪对制备的样品进行表征，未检测到衍射峰，表明材料未结晶。
对比例3
1.基底材料及处理同实施例1。
2.称取300mg二硫化锡颗粒用于蒸发，在0.3Pa的真空度条件下对二硫化锡颗粒进行蒸发，加热电流为10A。将蒸发好的薄膜放置到氮气保护的管式炉中进行热处理，温度为450℃，处理时间为30min。完成后，自然冷却至室温。肉眼可见黄色薄膜消失，说明在450℃该薄膜已经分解或者大量挥发。
Claims (1)
1.一种基于(001)晶面取向的二硫化锡薄膜的光电探测器件，其特征在于：包括所述的二硫化锡薄膜，和平行设在二硫化锡薄膜上的两个电极；
所述的电极为金电极；两个电极间距为220微米；
基底材料为聚酰亚胺塑料，由此构成柔性光电探测器件；
所述的二硫化锡晶态薄膜具有(001)晶面方向取向性，二硫化锡薄膜包括基底，基底材料为聚酰亚胺塑料；在基底材料表面蒸发沉积一层二硫化锡薄膜前驱体，压力0.3Pa，加热电流为10A，在惰性气氛保护的条件下对薄膜进行250℃热处理，获得具有(001)晶面方向取向性的二硫化锡晶态薄膜；所述惰性气氛保护的条件中，气氛为氮气、氩气；所述的热处理时间为30min以上；
所述的光电探测器件的制备方法依此如下：
(1)、利用蒸发的方法在经清洁处理过的基底材料表面蒸镀一层二硫化锡薄膜；
(2)、将上述样品放置到惰性气氛保护的条件下250℃热处理，自然冷却后取出；
(3)、在热处理过的样品上利用热蒸发的方法制备两个电极，构成平行式的光电导型。
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