CN106711200A - 一种p型ZnRhMO非晶氧化物半导体薄膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种p型ZnRhMO非晶氧化物半导体薄膜,其中,在所述ZnRhMO中,Zn为+2价,Rh为+3价,二者与O结合共同形成材料的p型导电基体;M为Cu、Ni、Sn的一种,为亚氧化化学价态,即当M为Cu时,其为+1价;M为Ni时,为+2价;M为Sn时,为+2价;M掺入基体中,形成p型导电,且M与Zn和Rh共同作用形成空间网络结构,在非晶状态下彼此连通,起到空穴传输通道的作用。本发明还公开了一种制备p型ZnRhCuO非晶氧化物半导体薄膜的方法,以烧结的ZnRhCuO陶瓷片为靶材,采用脉冲激光沉积法制得p型ZnRhCuO非晶薄膜,其空穴浓度为1013~1015cm‑3,可见光透过率≧87%。本发明所公开的p型ZnRhMO非晶氧化物半导体薄膜可用于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ZnRhMO非晶氧化物半导体薄膜,其中M为Cu、Ni、Sn,在ZnRhMO中为亚氧化化学价态。在p型ZnRhMO体系中:Zn为+2价,Rh为+3价,二者与O结合共同形成材料的p型导电基体;M为亚氧化化学价态,如Cu为+1价、Ni为+2价、Sn为+2价,M掺入基体中,形成p型导电,且M与Zn和Rh共同作用形成空间网络结构,在非晶状态下彼此连通,因而起到空穴传输通道的作用。
本发明所述的一种p型ZnRhMO非晶氧化物半导体薄膜,其特征在于:在ZnRhMO中,Zn为+2价,Rh为+3价,M为Cu、Ni、Sn中的一种,M为亚氧化化学价态;ZnRhMO薄膜为非晶态,具有p型导电特性。
本发明所提供的p型ZnRhMO非晶氧化物半导体薄膜,进一步,M为Cu,此时ZnRhMO即为ZnRhCuO,p型ZnRhCuO薄膜化学式为ZnxRh2CuyOx+3+0.5y,其中1≦x≦2,0.5≦y≦1。
本发明还提供了制备上述p型ZnRhCuO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、Rh2O3和Cu2O粉末为原材料,混合,研磨,在1050~1100℃的N2气氛下烧结,制成ZnRhCuO陶瓷片为靶材,其中Zn、Rh、Cu三组分的原子比为(1~2):2:(0.5~1);
(2)采用脉冲激光沉积(PLD)方法,将衬底和靶材安装在PLD反应室中,抽真空至真空度低于1×10-3Pa;
(3)通入O2为工作气体,气体压强10~13Pa,衬底温度为25~500℃,以脉冲激光轰击靶材,靶材表面原子和分子熔蒸后在衬底上沉积,形成一层薄膜,在不高于100Pa的O2气氛中自然冷却到室温,得到p型ZnRhCuO非晶薄膜。
采用上述方法生长的p型ZnRhCuO非晶氧化物半导体薄膜,其性能指标为:ZnRhCuO非晶薄膜具有p型导电特性,空穴浓度1013~1015cm-3,可见光透过率≧87%。
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ZnRhCuO材料,也无法获得具有p型导电且为非晶态的ZnRhCuO薄膜。
在p型ZnRhMO体系中,Zn与Rh与O结合共同形成材料的p型导电基体,M为Cu、Ni、Sn中的一种,为亚氧化化学价态,M掺入基体中,形成p型导电,且M与Zn和Rh共同作用可形成空间网络结构,在非晶状态下也可彼此连通,因而起到空穴传输通道的作用。除M为Cu外,当M为上述所述的其它元素时,也具有同样的机理,具有类似的性质,除ZnRhCuO之外的其它的p型ZnRhMO非晶氧化物半导体薄膜同样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ZnRhMO非晶氧化物半导体薄膜,其中Zn与Rh与O结合共同形成材料的p型导电基体,M在材料中也可形成p型导电,且起到空穴传输通道的作用,基于上述原理,ZnRhMO是一种良好的p型AOS材料。
2)本发明所述的p型ZnRhMO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ZnRhMO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ZnRhMO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ZnRhMO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ZnRhMO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ZnRhMO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、Rh2O3和Cu2O粉末为原材料,混合,研磨,在1100℃的N2气氛下烧结,制成ZnRhCuO陶瓷片为靶材,其中Zn、Rh、Cu三组分的原子比为1:2:0.5;
(2)采用脉冲激光沉积(PLD)方法,将衬底和靶材安装在PLD反应室中,抽真空至真空度9×10-4Pa;
(3)通入O2为工作气体,气体压强10Pa,衬底温度为25℃,以脉冲激光轰击靶材,靶材表面原子和分子熔蒸后在衬底上沉积,形成一层薄膜,便得到p型ZnRh2Cu0.5O4.25非晶薄膜。
以石英为衬底,按照上述生长步骤制得p型ZnRh2Cu0.5O4.25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43nm;具有p型导电特性,空穴浓度1013cm-3;可见光透过率87%。
实施例2
(1)以高纯ZnO、Rh2O3和Cu2O粉末为原材料,混合,研磨,在1100℃的N2气氛下烧结,制成ZnRhCuO陶瓷片为靶材,其中Zn、Rh、Cu三组分的原子比为1.5:2:1;
(2)采用脉冲激光沉积(PLD)方法,将衬底和靶材安装在PLD反应室中,抽真空至真空度9×10-4Pa;
(3)通入O2为工作气体,气体压强12Pa,衬底温度为250℃,以脉冲激光轰击靶材,靶材表面原子和分子熔蒸后在衬底上沉积,形成一层薄膜,在100Pa的O2气氛中自然冷却到室温,得到p型ZnRh2Cu0.5O4.25非晶薄膜。
以石英为衬底,按照上述生长步骤制得p型Zn1.5Rh2CuO5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52nm;具有p型导电特性,空穴浓度1014cm-3;可见光透过率89%。
实施例3
(1)以高纯ZnO、Rh2O3和Cu2O粉末为原材料,混合,研磨,在1050℃的N2气氛下烧结,制成ZnRhCuO陶瓷片为靶材,其中Zn、Rh、Cu三组分的原子比为2:2:1;
(2)采用脉冲激光沉积(PLD)方法,将衬底和靶材安装在PLD反应室中,抽真空至真空度9×10-4Pa;
(3)通入O2为工作气体,气体压强13Pa,衬底温度为500℃,以脉冲激光轰击靶材,靶材表面原子和分子熔蒸后在衬底上沉积,形成一层薄膜,在70Pa的O2气氛中自然冷却到室温,得到p型Zn2Rh2CuO5.5非晶薄膜。
以石英为衬底,按照上述生长步骤制得p型Zn2Rh2CuO5.5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67nm;具有p型导电特性,空穴浓度1015cm-3;可见光透过率91%。
上述各实施例中,使用的原料ZnO粉末、Rh2O3粉末和Cu2O粉末的纯度均在99.99%以上。
本发明p型ZnRhCuO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ZnRhMO体系中,M为Cu、Ni、Sn中的一种。除M为Cu外,当M为上述所述的其它元素时,也具有同样的机理,具有类似的性质,除ZnRhCuO之外的其它的p型ZnRhMO非晶氧化物半导体薄膜同样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ZnRhMO非晶氧化物半导体薄膜,其特征在于:在所述ZnRhMO中,Zn为+2价,Rh为+3价,二者与O结合共同形成材料的p型导电基体; M为Cu、Ni、Sn的一种,在所述ZnRhMO中为亚氧化化学价态,即当M为Cu时,其为+1价;M为Ni时,为+2价;M为Sn时,为+2价;M掺入基体中,形成p型导电,且M与Zn和Rh共同作用形成空间网络结构,在非晶状态下彼此连通,起到空穴传输通道的作用。
2.根据权利要求1所述的一种p型ZnRhMO非晶氧化物半导体薄膜,其特征在于: M为Cu,即所述ZnRhMO为ZnRhCuO,且p型ZnRhCuO非晶氧化物半导体薄膜的化学式为ZnxRh2CuyOx+3+0.5y,其中1≦x≦2,0.5≦y≦1。
3.根据权利要求2所述的一种p型ZnRhMO非晶氧化物半导体薄膜,其特征在于:所述p型ZnRhCuO非晶氧化物半导体薄膜的空穴浓度为1013~1015cm-3,可见光透过率≧87%。
4.如权利要求2或3所述的一种p型ZnRhMO非晶氧化物半导体薄膜的制备方法,其特征在于:制备 p型ZnRhCuO非晶氧化物半导体薄膜的步骤包括如下:
1)以高纯ZnO、Rh2O3和Cu2O粉末为原材料,混合,研磨,在1050~1100℃的N2气氛下烧结,制成ZnRhCuO陶瓷片为靶材,其中Zn、Rh、Cu三组分的原子比为1~2:2:0.5~1;
2)采用脉冲激光沉积(PLD)方法,将衬底和靶材安装在PLD反应室中,抽真空至真空度低于1×10-3Pa;
3)通入O2为工作气体,气体压强10~13Pa,衬底温度为25~500℃,以脉冲激光轰击靶材,靶材表面原子和分子熔蒸后在衬底上沉积,形成一层薄膜,在不高于100Pa的O2气氛中自然冷却到室温,得到p型ZnRhCuO非晶薄膜。
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