CN111206236B - 一种Mg掺杂GaN纳米线结构的制备方法 - Google Patents

一种Mg掺杂GaN纳米线结构的制备方法 Download PDF

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CN111206236B
CN111206236B CN202010024893.9A CN202010024893A CN111206236B CN 111206236 B CN111206236 B CN 111206236B CN 202010024893 A CN202010024893 A CN 202010024893A CN 111206236 B CN111206236 B CN 111206236B
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王如志
杨孟骐
梁琦
严辉
张铭
王波
王长昊
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Abstract

本发明涉及一种Mg掺杂GaN纳米线结构的制备方法。本发明提出采用元素掺杂的方法实现了GaN纳米线制备及其结构与形貌的调控。本发明采用MPCVD系统，以N2为N源，Ga2O3作为Ga源，MgO作为掺杂源，选择合适的还原剂防止氧化，选择合适工艺参数，通过调控Mg：Ga原子比例，可实现所制备的GaN纳米线截面在三方、四方及六方形结构进行调控。通过Mg掺杂调控实现了在常规GaN纳米线制备方法难以获得的四方形GaN纳米线，所制备的纳米线具有良好的结晶质量，在新型的GaN纳米线光电器件上具有良好的应用前景。

Description

一种Mg掺杂GaN纳米线结构的制备方法
技术领域
本发明涉及一种Mg掺杂GaN纳米线结构的制备方法，属于纳米材料的制备领域。
背景技术
氮化镓(GaN)是研制微电子器件、光电子器件的典型第三代半导体材料。它具有宽禁带，高的热导率，高化学稳定性等优异的物理和化学性质，其研究与应用是目前全球半导体研究的前沿和热点。GaN为六方纤锌矿结构，目前已经制备出截面形貌为三角形或六边形结构的GaN纳米线，而其他形貌纳米线比较难进行调控。目前对于GaN纳米线形貌调控的手段多为调节衬底种类、催化剂种类等，而缺少通过掺杂实现对GaN纳米线形貌进行调控的相关研究。
Mg掺杂的GaN材料主要使用分子束外延(MBE)和金属有机化学气相沉积(MOCVD)方法制备，但这两种方法大多使用有毒的NH3作为N源，金属有机气体作为Ga源和Mg源，对环境危害大，制备成本昂贵，所制备出的纳米线形貌多为六边形，缺少对其形貌调控研究；采用简单CVD设备制备Mg掺杂GaN纳米线，纳米线形貌均一性差，并且较难控制纳米线生长方向，不易制备高质量Mg掺杂GaN纳米线。
因此，探索一种绿色高效、形貌可控、重复性好的Mg掺杂GaN纳米线制备工艺变得尤为重要。
发明内容
本发明是的目的是提供一种Mg掺杂GaN纳米线结构的制备方法，其特征在于，包括以下步骤：
(1)、按照MgO、Ga2O3及活性碳粉末摩尔份数比：MgO 0.2-2份、Ga2O31份、活性碳粉末12份混合形成均匀粉体；
(2)将以上粉体放入球磨机进行球磨，球磨机转速200-500rpm，球磨时间1小时以上，最终产物即为制备GaN纳米线前驱粉体；
(3)将以上粉体放置于MPCVD系统的坩埚中，将预先制备表面溅射10-25nm的Au催化剂的Si衬底置于坩埚正上方，并扣上石英罩，通入10-40sccm流速的N2，保持腔体压力为10Torr，微波功率300W，在850-1100℃条件下生长20-60min，衬底表面的黄色物质即为所获得的GaN纳米线产物。
进一步，通过改变前驱粉体中MgO和Ga2O3摩尔比，即可实现Mg掺杂的同时改变所制备的GaN纳米线截面形貌，MgO：Ga2O3为0.2:1-0.5:1时纳米线截面形貌为三方形(MgO：Ga2O3为0.5:1的临界点附近，纳米线截面形貌为三方形向四方形过渡)，MgO：Ga2O3为0.5:1-1.5:1时纳米线截面形貌为四方形(MgO：Ga2O3为1.5:1的临界点附近，纳米线截面形貌为四方形向六方形过渡)，MgO：Ga2O3为1.5:1-2:1时纳米线截面形貌为六方形。
进一步，坩埚材质为石墨；坩埚内径宽于衬底20mm以上，加入前驱粉体后，粉体距离衬底5mm-20mm。
本发明有以下优点和效益：
(1)本发明采用MPCVD设备制备GaN纳米线其并采用Mg掺杂调控结构形貌，相较未掺杂GaN纳米线，Mg掺杂纳米线直径由80nm增长至300nm以上，纳米线截面在三方、四方及六方形之间进行调控。
(2)进一步，本发明采用N2取代有毒的NH3作为反应的氮源，采用MgO和Ga2O3作为Mg源和Ga源，摒弃了有机金属气源对于环境的危害。
(3)进一步，本发明采用微波增强等离子体设备将N2作为唯一气体源，而不会因为有H离子的引入而降低了Mg掺杂GaN纳米线的性能。
(4)进一步，本发明制备Mg掺杂GaN纳米线，通过调控MgO的摩尔比例，可以对纳米线表面形貌进行改变，Mg元素的引入使纳米线表面出现层状锯齿形结构，有利于提升场发射，电催化等性能。
(5)进一步，本发明采用石墨作为坩埚材料，提高升温速率的同时也提高了对于前驱粉体的还原效率。
附图说明
图1、实施例1制备GaN纳米线的SEM图谱。
图2、实施例2制备Mg掺杂GaN纳米线的SEM图谱。
图3、实施例3制备Mg掺杂GaN纳米线的SEM图谱。
图4、实施例4制备Mg掺杂GaN纳米线的SEM图谱。
图5、实施例1和实施例3制备GaN纳米线的XRD图谱。
图6、实施例3制备Mg掺杂GaN纳米线的EDS图谱。
图7、实施例3制备Mg掺杂GaN纳米线的HRTEM图谱和SAED图谱。
具体实施方式：
下面通过实施例对本发明进行进一步说明，本发明绝非局限于所述实施例。
实施例1
MgO、Ga2O3和活性碳粉末摩尔比例0.2:1:12的粉末混合均匀并放入球磨机进行300rpm球磨2小时，称取0.25g放入石墨舟中，将预先制备表面溅射10nm的Au催化剂的Si衬底放置在石墨舟顶部正上方，距离下方粉末约为5mm。然后把石墨舟转移到MPCVD的加热台的中心，将一枚上方开口石英罩扣置在石墨舟上方；通入13sccm流速的N2，保持腔体压力为10Torr，衬底加热温度为875℃，微波功率300W，在等离子条件进行GaN线生长，反应时间30min得到纳米线。
所制备GaN扫描电镜图谱如图1所示，纳米线直径约为60-100nm，长度20-30μm，形貌为细长的三角锥状纳米线，纳米线表面光滑，没有出现弯曲扭折。图5为GaN纳米线的XRD图谱，可以观察到纳米线结晶性较为良好，在32.3°，34.5°和36.8°的GaN特征峰比较明显。
实施例2
MgO、Ga2O3和活性碳粉末摩尔比例0.5:1:12的粉末加混合均匀并放入球磨机进行300rpm球磨2小时，称取0.25g放入石墨舟中，将预先制备表面溅射10nm的Au催化剂的Si衬底放置在石墨舟顶部正上方，距离下方粉末约为5mm。然后把石墨舟转移到MPCVD的加热台的中心，将一枚上方开口石英罩扣置在石墨舟上方；通入13sccm流速的N2，保持腔体压力为10Torr，衬底加热温度为875℃，微波功率300W，在等离子条件进行GaN线生长，反应时间30min得到纳米线。
所制备GaN扫描电镜图谱如图2所示，纳米线直径约为300-350nm，长度20-30μm，纳米线形貌延孪晶界分为两侧，一侧为三棱柱状结构，另一侧为三角形阶梯状生长结构，纳米线表面有层错状边缘，但其顶端为三角形金字塔结构，纳米线截面形貌由三角形向四边形转变。
实施例3
MgO、Ga2O3和活性碳粉末摩尔比例1:1:12的粉末混合均匀并放入球磨机进行300rpm球磨2小时，称取0.25g放入石墨舟中，将预先制备表面溅射10nm的Au催化剂的Si衬底放置在石墨舟顶部正上方，距离下方粉末约为5mm。然后把石墨舟转移到MPCVD的加热台的中心，将一枚上方开口石英罩扣置在石墨舟上方；通入13sccm流速的N2，保持腔体压力为10Torr，衬底加热温度为875℃，微波功率300W，在等离子条件进行GaN线生长，反应时间30min得到纳米线。
所制备GaN扫描电镜图谱如图3所示，纳米线直径约为350-400nm，长度20-30μm，纳米线形貌为四边形堆叠结构，纳米线表面层错状边缘比较均一，其顶端为四边形金字塔结构，纳米线保持笔直生长。图5为Mg掺杂GaN纳米线的XRD图谱，可以观察到纳米线结晶性较为良好，在32.3°，34.5°和36.8°的GaN特征峰比较明显，但其峰值强度略低于实施例1样品。图6为纳米线EDS图谱，Mg原子与Ga原子比约为5.91:94.09，表明有Mg元素掺杂进入GaN纳米线中。图7为纳米线TEM图谱，与生长方向垂直方向晶面间距为0.258nm，近似于GaN的(002)方向晶面间距，通过SAED图可知，其衍射光斑夹角61.4°，生长方向为<0-110>方向，而衍射光斑排列清晰均匀表面纳米线有较好的结晶性。
实施例4
MgO、Ga2O3和活性碳粉末摩尔比例2:1:12的粉末混合均匀并放入球磨机进行300rpm球磨2小时，称取0.25g放入石墨舟中，将预先制备表面溅射10nm的Au催化剂的Si衬底放置在石墨舟顶部正上方，距离下方粉末约为5mm。然后把石墨舟转移到MPCVD的加热台的中心，将一枚上方开口石英罩扣置在石墨舟上方；通入40sccm流速的N2，保持腔体压力为10Torr，衬底加热温度为900℃，微波功率300W，在等离子条件进行GaN线生长，反应时间50min得到纳米线。
所制备GaN扫描电镜图谱如图4所示，纳米线直径约为1300-1400nm，长度30-40μm，纳米线截面形貌为六方结构，纳米线表面层错状边缘不均一。

Claims (2)

1.一种Mg 掺杂GaN 纳米线结构的制备方法，其特征在于，包括以下步骤：
（1）、按照MgO、Ga2O3及活性碳粉末摩尔份数比：MgO 1 份、Ga2O3 1份、活性碳粉末12 份混合形成均匀粉体；
（2）将以上粉体放入球磨机进行球磨，球磨机转速200-500rpm，球磨时间1 小时以上，最终产物即为制备GaN 纳米线前驱粉体；
（3）将GaN 纳米线前驱粉体放置于MPCVD 系统的坩埚中，将预先制备表面溅射厚度为10-25nm 的Au 催化剂的Si 衬底置于坩埚正上方，并扣上石英罩，通入10-40sccm 流速的N2，保持腔体压力为10Torr，微波功率300W，在850-1100℃条件下生长20-60min，衬底表面的黄色物质即为纳米线截面形貌为四方形的GaN纳米线产物，纳米线直径为350-400nm，长度20-30μm。
2.根据权利要求1 所述的制备方法，其特征在于：步骤（3）中，坩埚材质为石墨；坩埚内径宽于衬底20mm 以上，加入GaN 纳米线前驱粉体后，GaN纳米线前驱粉体距离衬底5mm-20mm。
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