CN106711195A - 一种p型ZnMSnO非晶氧化物半导体薄膜及其制备方法 - Google Patents
一种p型ZnMSnO非晶氧化物半导体薄膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种p型ZnMSnO非晶氧化物半导体薄膜，所述ZnMSnO中的M元素为过渡金属元素、且自身的氧化物为p型导电，为Cu、Ni、Ag、Au、Fe、Co、Mn元素中的一种，在所述ZnMSnO中M元素为自身的最低价态；所述ZnMSnO中，Zn为+2价，为材料的基体元素；M为最低价态，掺入基体形成p型导电；Sn为+2价，具有球形电子轨道，在非晶状态下电子云高度重合，起到空穴传输通道的作用。本发明还公开了制备p型ZnCuSnO非晶氧化物半导体薄膜的方法，以ZnCuSnO陶瓷片为靶材，采用射频磁控溅射法，制得的p型ZnCuSnO非晶薄膜的空穴浓度1015~1016cm‑3，可见光透过率≧85%。本发明所制备的薄膜可以用于P型非晶薄膜晶体管。
Description
技术领域
本发明涉及一种非晶氧化物半导体薄膜，尤其涉及一种p型非晶氧化物半导体薄膜及其制备方法。
背景技术
薄膜晶体管（TFT）是微电子特别是显示工程领域的核心技术之一。目前，TFT主要是基于非晶硅（a-Si）技术，但是a-Si TFT是不透光的，光敏性强，需要加掩膜层，显示屏的像素开口率低，限制了显示性能，而且a-Si迁移率较低（~2 cm2/Vs），不能满足一些应用需求。基于多晶硅（p-Si）技术的TFT虽然迁移率高，但是器件均匀性较差，而且制作成本高，这限制了它的应用。此外，有机半导体薄膜晶体管（OTFT）也有较多的研究，但是OTFT的稳定性不高，迁移率也比较低（~1 cm2/Vs），这对其实际应用是一个较大制约。
为解决上述问题，人们近年来开始致力于非晶氧化物半导体（AOS）TFT的研究，其中最具代表性的是InGaZnO。与Si基TFT不同，AOS TFT具有如下优点：可见光透明，光敏退化性小，不用加掩膜层，提高了开口率，可解决开口率低对高分辨率、超精细显示屏的限制；易于室温沉积，适用于有机柔性基板；迁移率较高，可实现高的开/关电流比，较快的器件响应速度，应用于高驱动电流和高速器件；特性不均较小，电流的时间变化也较小，可抑制面板的显示不均现象，适于大面积化用途。
由于金属氧化物特殊的电子结构，氧原子的2p能级一般都远低于金属原子的价带电子能级，不利于轨道杂化，因而O 2p轨道所形成的价带顶很深，局域化作用很强，因而空穴被严重束缚，表现为深受主能级，故此，绝大多数的氧化物本征均为n型导电，具有p型导电特性的氧化物屈指可数。目前报道的p型导电氧化物半导体主要为SnO、NiO、Cu2O、CuAlO2等为数不多的几种，但这些氧化物均为晶态结构，不是非晶形态。目前人们正在研究的AOS如InGaZnO等均为n型半导体，具有p型导电的非晶态氧化物半导体几乎没有。因而，目前报道的AOS TFT均为n型沟道，缺少p型沟道的AOS TFT，这对AOS TFT在新一代显示、透明电子学等诸多领域的应用产生了很大的制约。因而，设计和寻找并制备出p型导电的非晶氧化物半导体薄膜是人们亟需解决的一个难题。
发明内容
本发明针对实际应用需求，拟提供一种p型非晶氧化物半导体薄膜及其制备方法。
本发明提供了一种p型ZnMSnO非晶氧化物半导体薄膜，其中M具有下述共性：为过渡金属元素，自身的氧化物为p型导电，掺入ZnO基体提供空穴，包括Cu、Ni、Ag、Au、Fe、Co、Mn七种元素。在p型ZnMSnO体系中：Zn为+2价，为材料的基体元素；M为最低价态，掺入基体形成p型导电，且具有一定的空穴浓度的控制作用；Sn为+2价，在材料中也可提供p型导电，且具有球形电子轨道，在非晶状态下电子云高度重合，起到空穴传输通道的作用。
本发明所提供的p型ZnMSnO非晶氧化物半导体薄膜，在ZnMSnO中，Zn为+2价，M元素为Cu、Ni、Ag、Au、Fe、Co、Mn中的一种，且均为其最低价态，Sn为+2价；ZnMSnO薄膜为非晶态，具有p型导电特性。
本发明所述的一种p型ZnMSnO非晶氧化物半导体薄膜，具体的，进一步地，M为Cu，此时ZnMSnO即为ZnCuSnO，如各实施例具体阐述的，p型ZnCuSnO薄膜化学式为ZnCuxSnyO1+0.5x+y，其中0.2≦x≦0.3，0.3≦y≦0.5。
本发明还提供了制备上述p型ZnCuSnO非晶氧化物半导体薄膜的制备方法，具体步骤如下：
（1）以高纯ZnO、Cu2O和SnO粉末为原材料，混合，研磨，在1000℃的N2气氛下烧结，制成ZnCuSnO陶瓷片为靶材，其中Zn、Cu、Sn三组分的原子比为1:(0.2~0.3):(0.3~0.5)；
（2）采用射频磁控溅射方法，将衬底和靶材安装在溅射反应室中，抽真空至不高于1×10-3Pa；
（3）通入Ar-O2为工作气体，气体压强1.1~1.2Pa，Ar-O2流量体积比为10:2~10:3，溅射功率120~130W，衬底温度为25~300℃，在Ar-O2离子的轰击下，靶材表面原子和分子溅射出来，在衬底上沉积形成一层薄膜，在Ar气氛下自然冷却到室温，得到p型ZnCuSnO非晶薄膜。
采用上述方法生长的p型ZnCuSnO非晶氧化物半导体薄膜，其性能指标为：ZnCuSnO非晶薄膜具有p型导电特性，空穴浓度1015~1016cm-3，可见光透过率≧85%。
上述材料参数和工艺参数为发明人经多次实验确立的，需要严格控制，在发明人的实验中若超出上述参数的范围，则无法实现设计的p型ZnCuSnO材料，也无法获得具有p型导电且为非晶态的ZnCuSnO薄膜。
在p型ZnMSnO体系中，M具有下述共性：为过渡金属元素，自身的氧化物为p型导电，掺入ZnO基体提供空穴，在体系中具有最低的化学价态。当M为Ni、Ag、Au、Fe、Co、Mn时，与M为Cu具有同样的机理，也具有类似的性质，除ZnCuSnO之外的其它的p型ZnMSnO非晶氧化物半导体薄膜能用上述类似的方法与步骤进行制备，所得的材料和器件具有类似的性能。
本发明的有益效果在于：
1）本发明所述的p型ZnMSnO非晶氧化物半导体薄膜，其中Zn为材料的基体元素，M掺入基体形成p型导电，且具有空穴浓度的控制作用，Sn起到空穴传输通道的作用，基于上述原理，ZnMSnO是一种良好的p型AOS材料。
2）本发明所述的p型ZnMSnO非晶氧化物半导体薄膜，具有良好的材料特性，其p型导电性能易于通过组分比例实现调控。
3）本发明所述的p型ZnMSnO非晶氧化物半导体薄膜，可以作为沟道层制备的p型AOS TFT，从而为p型AOS TFT的应用提供关键材料。
4）本发明所述的p型ZnMSnO非晶氧化物半导体薄膜，与已存在的n型InGaZnO非晶氧化物半导体薄膜组合，可形成一个完整的AOS的p-n体系，且p型ZnMSnO与n型InGaZnO均为透明半导体材料，因而可制作透明光电器件和透明逻辑电路，开拓AOS在透明电子产品中应用，促进透明电子学的发展。
5）本发明所述的p型ZnMSnO非晶氧化物半导体薄膜，可在室温下生长，与有机柔性衬底相兼容，因而可在可穿戴、智能化的柔性产品中获得广泛应用。
6）本发明所述的p型ZnMSnO非晶氧化物半导体薄膜，在生长过程中存在较宽的参数窗口，可实现大面积室温沉积，能耗低，制备工艺简单、成本低，可实现工业化生产。
具体实施例
以下结合具体实施例进一步说明本发明。
实施例1
（1）以高纯ZnO、Cu2O和SnO粉末为原材料，混合，研磨，在1000℃的N2气氛下烧结，制成ZnCuSnO陶瓷片为靶材，其中Zn、Cu、Sn三组分的原子比为1:0.2:0.3；
（2）采用射频磁控溅射方法，将衬底和靶材安装在溅射反应室中，抽真空至1×10-3Pa；
（3）通入Ar-O2为工作气体，气体压强1.1Pa，Ar-O2流量体积比为10:2，溅射功率120W，衬底温度为25℃，在Ar-O2离子的轰击下，靶材表面原子和分子溅射出来，在衬底上沉积形成一层薄膜，便得到p型ZnCu0.2Sn0.3O1.4非晶薄膜。
以石英为衬底，按照上述生长步骤制得p型ZnCu0.2Sn0.3O1.4薄膜，对其进行结构、电学和光学性能测试，测试结果为：薄膜为非晶态，厚度50nm；具有p型导电特性，空穴浓度1015cm-3；可见光透过率85%。
实施例2
（1）以高纯ZnO、Cu2O和SnO粉末为原材料，混合，研磨，在1000℃的N2气氛下烧结，制成ZnCuSnO陶瓷片为靶材，其中Zn、Cu、Sn三组分的原子比为1:0.25:0.4；
（2）采用射频磁控溅射方法，将衬底和靶材安装在溅射反应室中，抽真空至1×10-3Pa；
（3）通入Ar-O2为工作气体，气体压强1.1Pa，Ar-O2流量体积比为10:2，溅射功率120W，衬底温度为150℃，在Ar-O2离子的轰击下，靶材表面原子和分子溅射出来，在衬底上沉积形成一层薄膜，便得到p型ZnCu0.25Sn0.4O1.525非晶薄膜。
以石英为衬底，按照上述生长步骤制得p型ZnCu0.25Sn0.4O1.525薄膜，对其进行结构、电学和光学性能测试，测试结果为：薄膜为非晶态，厚度56nm；具有p型导电特性，空穴浓度1015cm-3；可见光透过率86%。
实施例3
（1）以高纯ZnO、Cu2O和SnO粉末为原材料，混合，研磨，在1000℃的N2气氛下烧结，制成ZnCuSnO陶瓷片为靶材，其中Zn、Cu、Sn三组分的原子比为1:0.3:0.5；
（2）采用射频磁控溅射方法，将衬底和靶材安装在溅射反应室中，抽真空至1×10-3Pa；
（3）通入Ar-O2为工作气体，气体压强1.2Pa，Ar-O2流量体积比为10:3，溅射功率130W，衬底温度为300℃，在Ar-O2离子的轰击下，靶材表面原子和分子溅射出来，在衬底上沉积形成一层薄膜，便得到p型ZnCu0.3Sn0.5O1.65非晶薄膜。
以石英为衬底，按照上述生长步骤制得p型ZnCu0.3Sn0.5O1.65薄膜，对其进行结构、电学和光学性能测试，测试结果为：薄膜为非晶态，厚度63nm；具有p型导电特性，空穴浓度1016cm-3；可见光透过率90%。
上述各实施例中，使用的原料ZnO粉末、Cu2O粉末和SnO粉末的纯度均在99.99%以上。
本发明p型ZnCuSnO非晶氧化物半导体薄膜制备所使用的衬底，并不局限于实施例中的石英片，其它各种类型的衬底均可使用。
在p型ZnMSnO体系中，M具有下述共性：为过渡金属元素，自身的氧化物为p型导电，掺入ZnO基体提供空穴，在体系中具有最低的化学价态。当M为Ni、Ag、Au、Fe、Co、Mn时，与M为Cu具有同样的机理、具有类似的性质，除ZnCuSnO之外的其它的p型ZnMSnO非晶氧化物半导体薄膜能用上述类似的方法与步骤进行制备，所得的材料和器件具有类似的性能。
Claims (4)
1.一种p型ZnMSnO非晶氧化物半导体薄膜，其特征在于：所述ZnMSnO中的M元素为过渡金属元素、且自身的氧化物为p型导电，为Cu、Ni、Ag、Au、Fe、Co、Mn元素中的一种，在所述ZnMSnO中M元素为自身的最低价态，；所述ZnMSnO中，Zn为+2价， Sn为+2价。
2.根据权利要求1所述的一种p型ZnMSnO非晶氧化物半导体薄膜，其特征在于： M为Cu元素，所述ZnMSnO即为ZnCuSnO， p型ZnCuSnO非晶薄膜的化学式为ZnCuxSnyO1+0.5x+y，其中0.2≦x≦0.3，0.3≦y≦0.5。
3.根据权利要求2所述的一种p型ZnMSnO非晶氧化物半导体薄膜，其特征在于：p型ZnCuSnO非晶薄膜的空穴浓度1015~1016cm-3，可见光透过率≧85%。
4.如权利要求2或3所述p型ZnMSnO非晶氧化物半导体薄膜的制备方法，其特征在于：制备p型ZnCuSnO非晶氧化物半导体薄膜包括步骤：
1）以高纯ZnO、Cu2O和SnO粉末为原材料，混合，研磨，在1000℃的N2气氛下烧结，制成ZnCuSnO陶瓷片为靶材，其中Zn、Cu、Sn三组分的原子比为1:0.2~0.):0.3~0.)；
2）采用射频磁控溅射方法，将衬底和靶材安装在溅射反应室中，抽真空至不高于1×10-3Pa；
3）通入Ar-O2为工作气体，气体压强1.1~1.2Pa，Ar-O2流量体积比为10:2~10:3，溅射功率120~130W，衬底温度为25~300℃，在Ar-O2离子的轰击下，靶材表面原子和分子溅射出来，在衬底上沉积形成一层薄膜，在Ar气氛下自然冷却到室温，得到p型ZnCuSnO非晶薄膜。
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| CN103173732A (zh) * | 2013-03-08 | 2013-06-26 | 北京航空航天大学 | 一种p型透明导电氧化物及其掺杂非晶薄膜的制备方法 |
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