CN103715325B - 单根ZnO微米线同质结发光二极管的制备方法 - Google Patents

单根ZnO微米线同质结发光二极管的制备方法 Download PDF

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CN103715325B
CN103715325B CN201310730886.0A CN201310730886A CN103715325B CN 103715325 B CN103715325 B CN 103715325B CN 201310730886 A CN201310730886 A CN 201310730886A CN 103715325 B CN103715325 B CN 103715325B
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micro wire
zno
powder
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oxygen
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CN103715325A (zh
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冯秋菊
唐凯
吕佳音
刘洋
李梦轲
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Jiangsu Xinhe Environmental Technology Co., Ltd
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Liaoning Normal University
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    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L33/0083—Processes for devices with an active region comprising only II-VI compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L33/0093—Wafer bonding; Removal of the growth substrate
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    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
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    • H01L33/28—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table

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Abstract

本发明公开一种单根ZnO微米线同质结发光二极管的制备方法，是采用简单的CVD方法通过控制生长时间等参数，首先在衬底上生长一层高取向的未掺杂n型ZnO微米线，然后在其上继续生长一层Sb掺杂的p型ZnO微米线，从而制备出ZnO微米线的同质结，再从样品衬底底部剥离出单根的微米线，在其两端做好电极，所得微米线直径为10~100μm，长度为1~20mm。不但制备过程简单、成本低，通过对该器件测试表明该器件具有良好的整流特性和极强的发光性能。

Description

单根ZnO微米线同质结发光二极管的制备方法
技术领域
本发明属于半导体器件领域，具体涉及一种用化学气相沉积（CVD）设备制备单根ZnO微米线同质结发光二极管的方法。
背景技术
ZnO是一种直接带隙宽禁带半导体材料，室温下禁带宽度为3.37eV，激子束缚能高达60meV，在光电、催化、传感以及生化等不同领域都有着广阔的应用前景。而纳/微米结构的ZnO具有比薄膜和体单晶更加优越的性能，如高的结晶质量和量子限域效应等，可以用于纳/微米紫外激光器、发光二极管、场发射晶体管等光电器件的制备，成为纳/微米半导体材料研究领域的新热点。ZnO的微米结构和纳米结构相比，由于其尺寸较大可以在肉眼或光学显微镜下进行操作，所以其相关器件的制作就更方便和容易，此外，单根微米线制成的发光器件在发光性能发面也要优于单根纳米线的发光器件。为了实现纳/微米结构的ZnO同质结光电器件的应用，n型和p型ZnO纳/微米材料的制备是必需的，由于ZnO是本征n型半导体材料，很容易获得n型ZnO，但是p型ZnO却很难制备。经过人们的大量努力，目前p型ZnO纳/微米材料的研究已经取得了一些进展。简单化学气相沉积（CVD）方法因不采用金属有机源，具有设备简单、价格低廉、生产成本低等一些优势，已广泛用于低维材料的制备。目前已有采用CVD方法制备p型ZnO纳米线和微米线以及纳米线的同质结发光二极管，但是由于受制备方法等因素的影响，迄今为止还没有单根ZnO微米线同质结发光二极管的相关报道。
发明内容
本发明是为了解决现有技术中所存在的上述技术问题，提供一种用化学气相沉积（CVD）设备制备单根ZnO微米线同质结发光二极管的方法。
本发明的技术解决方案是： 一种单根ZnO微米线同质结发光二极管的制备方法，其特征在于依次按如下步骤进行：
a.将纯度大于99%的ZnO粉末和C粉按照质量比1～10：1充分混合制成反应源材料，将反应源材料放入石英舟内，然后再将石英舟放入化学气相沉积系统石英管的中心处，衬底位于反应源材料下方1~30cm处；
b. 通入载气氩气，氩气流量为10~500ml/min，当温度加热至950~1100℃时，通入氧气，氧气流量为1~100ml/min，开始n型ZnO微米线的生长，生长时间为15～30分钟；
c. 关闭氧气、保持氩气流量，降温至400～700℃拔掉进气口处的石英帽，把石英舟取出；
d. 将纯度大于99%的ZnO粉末和C粉及纯度大于99.9%的Sb2O3粉末按照质量比20：3：1～10充分混合制成反应源材料，再将反应源材料放入另一石英舟内，然后再将此石英舟放入化学气相沉积系统石英管的中心处；
e. 当温度加热至950~1100℃时，通入氧气，氧气流量为1~100ml/min，开始p型ZnO微米线的生长，生长时间为20～40分钟；
f. 关闭氧气，保持氩气流量，降温至室温，取出样品；
g. 从样品衬底底部剥离出单根微米线，分别在单根微米线的两端制作电极，从而制成单根ZnO微米线同质结发光二极管。
所述生长温度均为1000℃；所述d步骤的纯度大于99%的ZnO粉末和C粉及纯度大于99.9%的Sb2O3粉末的质量比为20：3：5。
本发明是采用简单的CVD方法通过控制生长时间等参数，首先在衬底上生长一层高取向的未掺杂n型ZnO微米线，然后在其上继续生长一层Sb掺杂的p型ZnO微米线，从而制备出ZnO微米线的同质结，再从样品衬底底部剥离出单根的微米线，在其两端做好电极，所得微米线直径为10~100μm，长度为1~20mm。不但制备过程简单、成本低，通过对该器件测试表明该器件具有良好的整流特性和极强的发光性能。
附图说明
图1是本发明实施例1所得ZnO微米线同质p-n结的场发射扫描电子显微镜照片（FE-SEM）。
图2是本发明实施例1所得单根ZnO微米线同质结发光二极管的I-V曲线图。
图3是本发明实施例2所得ZnO微米线同质p-n结的场发射扫描电子显微镜照片（FE-SEM）。
图4是本发明实施例3所得ZnO微米线同质p-n结的场发射扫描电子显微镜照片（FE-SEM）。
图5是本发明实施例4所得单根ZnO微米线同质结发光二极管的电致发光照片。
具体实施方式
实施例1：
a.将纯度大于99%的ZnO粉末和C粉按照质量比2：1充分混合制成反应源材料，将反应源材料放入石英舟内，然后再将石英舟放入化学气相沉积系统生长室内的高温加热区，硅衬底位于反应源材料下方20cm处；
衬底可以采用氧化锌、氮化镓、蓝宝石、碳化硅、硅、砷化镓、磷化铟、氟化钙、石英、玻璃以及金属，也可以直接以化学气相沉积系统的石英管内壁为衬底；
b. 通入高纯度氩气为载气，氩气流量为50ml/min，当温度加热至1000℃时，通入氧气，氧气流量为25ml/min，开始n型ZnO微米线的生长，生长时间为15分钟；
c. 关闭氧气、保持氩气流量，降温至500℃拔掉进气口处的石英管帽，把反应完的装有ZnO粉末和C粉的石英舟取出；
d. 将纯度大于99%的ZnO粉末和C粉及纯度大于99.9%的Sb2O3粉末按照质量比20：3：3充分混合制成反应源材料，再将反应源材料放入另一石英舟内，然后再将此石英舟放入化学气相沉积系统生长室内的高温加热区；
e. 当温度加热至1000℃时，通入氧气，氧气流量为25ml/min，开始p型ZnO微米线的生长，生长时间为20分钟；
f. 关闭氧气，保持氩气流量，降温至室温，取出样品；
g. 用细牙签仔细从样品衬底底部剥离出单根微米线，放在干净的玻璃载玻片上，在微米线的两端分别点上导电银胶制成电极，从而制成单根ZnO微米线同质结发光二极管。
本发明实施例1在衬底上有大量的微米线生长出来，而且取向性非常好，都垂直于衬底表面。生长出的微米线直径大约为30μm，长度约为20mm，其扫描电镜照片如图1所示。此外，制成的单根ZnO微米线同质结发光二极管呈现出较好的整流特性，I-V曲线如图2所示。
实施例2：
方法与实施例1基本相同，与实施例1所不同的是两次生长温度均为950℃。所得样品的扫描电镜照片如图3所示。从图3中可以看出样品表面有一些微米线的生成，但是微米线的长度相对较短（5mm），取向性不及实施例1。
实施例3：
方法与实施例1基本相同，与实施例1所不同的是两次生长温度均为1100℃。所得样品的扫描电镜照片如图4所示。从图4中可以看出样品表面有大量的微米线的生成，但是微米线的长度相对较短（10mm），取向性亦不及实施例1。
实施例4：
方法与实施例1基本相同，与实施例1所不同的是d步骤的纯度大于99%的ZnO粉末和C粉及纯度大于99.9%的Sb2O3粉末的质量比为20：3：5，分别为20克3克和5克。所得制品的发光二极管的电致发光强度高，如图3所示。
对比实验表明：随着Sb含量的增加，微米线的长度开始变短，而且其直径和长度也开始变得不均匀，Sb含量是随着Sb2O3粉量的增加而有所增加。分别将实施例1、2、3、4实现了室温下的电致发光，其发光强度很强在亮室中就可以用肉眼清楚的观察到，在相同外加电压下，实施例4的电致发光发光强度要高于实施例1、2、3。

Claims (2)

1.一种单根ZnO微米线同质结发光二极管的制备方法，其特征在于依次按如下步骤进行：
a.将纯度大于99%的ZnO粉末和C粉按照质量比1～10：1充分混合制成反应源材料，将反应源材料放入石英舟内，然后再将石英舟放入化学气相沉积系统石英管的中心处，衬底位于反应源材料下方1~30cm处；
b. 通入载气氩气，氩气流量为10~500ml/min，当温度加热至950~1100℃时，通入氧气，氧气流量为1~100ml/min，开始n型ZnO微米线的生长，生长时间为15～30分钟；
c. 关闭氧气、保持氩气流量，降温至400～700℃拔掉进气口处的石英帽，把石英舟取出；
d. 将纯度大于99%的ZnO粉末和C粉及纯度大于99.9%的Sb2O3粉末按照质量比20：3：1～10充分混合制成反应源材料，再将反应源材料放入另一石英舟内，然后再将此石英舟放入化学气相沉积系统石英管的中心处；
e. 当温度加热至950~1100℃时，通入氧气，氧气流量为1~100ml/min，开始p型ZnO微米线的生长，生长时间为20～40分钟；
f. 关闭氧气，保持氩气流量，降温至室温，取出样品；
g. 从样品衬底底部剥离出单根微米线，分别在单根微米线的两端制作电极，从而制成单根ZnO微米线同质结发光二极管。
2.根据权利要求1所述的单根ZnO微米线同质结发光二极管的制备方法，其特征在于：所述生长温度为1000℃；所述d步骤的纯度大于99%的ZnO粉末和C粉及纯度大于99.9%的Sb2O3粉末的质量比为20：3：5。
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