CN113972299B - 一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法 - Google Patents

一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法 Download PDF

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CN113972299B
CN113972299B CN202111157718.8A CN202111157718A CN113972299B CN 113972299 B CN113972299 B CN 113972299B CN 202111157718 A CN202111157718 A CN 202111157718A CN 113972299 B CN113972299 B CN 113972299B
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CN113972299A (zh
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李国强
陈�胜
王文樑
柴吉星
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South China University of Technology SCUT
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Abstract

本发明公开了一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法，所述方法包括：用丙酮、乙醇和去离子水对衬底进行表面清洗；其中，所述衬底材料为Si/SiO2衬底或SiO2玻璃衬底；在所述衬底上进行光刻，旋涂光刻胶，进行光刻后再经过干法刻蚀或湿法腐蚀获得凹槽图形；在所述衬底的凹槽图形中沉积一层锗晶体，得到处理后的衬底；将所述处理后的衬底放进化学气相沉积设备中进行生长，生长源为高纯度硫粉和高纯度锗粉，从而制得SiO2衬底上的硫化锗单晶薄膜。本发明提供的制备方法操作简单，可以在SiO2衬底上生长出单晶硫化锗GeS2，单晶硫化锗晶体质量高，表面粗糙度小，具有对应可见光波段蓝紫光的禁带宽度。

Description

一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法
技术领域
本发明涉及宽禁带光电探测半导体材料生长技术领域，具体涉及一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法。
背景技术
硫化锗(GeS2)是一种高禁带宽度层状面内各向异性的四族硫系化合物半导体，其晶体结构为单斜结构，由四面体基本单元组成层状分子，层与层之间由范德华力相结合。由于这种独特的面内各向异性结构，硫化锗具有光电各向异性和电致相变等独特性能，在偏振光探测器、忆阻器、光存储器和高比能电池中得到广泛应用。目前硫化锗晶体生长常用的方法是化学气相传输法(CVT)：将高纯硫粉和高纯锗粉按照一定比例融封在石英管中，在1000℃生长24h得到硫化锗块状晶体。这种方法需要较长的生长时间，得到的晶体为大的块体，不利于加工制备成器件。
为了将硫化锗(GeS2)更好的应用到器件，与硅基器件单片集成，需要一种将硫化锗(GeS2)生长在硅基衬底上的简单方法。
发明内容
为了解决上述现有技术的不足，本发明提供了一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法，采用该制备方法可以在SiO2衬底上生长出单晶硫化锗GeS2，制备的单晶硫化锗晶体质量高，表面粗糙度小，具有对应可见光波段蓝紫光的禁带宽度。
本发明的目的可以通过采取如下技术方案达到：
一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法，所述方法包括：
用丙酮、乙醇和去离子水对衬底进行表面清洗；其中，所述衬底材料为Si/SiO2衬底或SiO2玻璃衬底；
在所述衬底上进行光刻，旋涂光刻胶，进行光刻后再经过干法刻蚀或湿法腐蚀获得凹槽图形；
在所述衬底的凹槽图形中沉积一层锗晶体，得到处理后的衬底；
将所述处理后的衬底放进化学气相沉积设备中进行生长，生长源为高纯度硫粉和高纯度锗粉，从而制得SiO2衬底上的硫化锗单晶薄膜。
进一步的，所述湿法腐蚀包括BOE溶液或食人鱼溶液，所述干法刻蚀包括电感耦合等离子体刻蚀。
进一步的，所述在所述衬底的凹槽图形中沉积一层锗晶体，采用的方法为电子束蒸镀、激光脉冲沉积、物理气相沉积物理溅射、物理气相沉积和化学气相沉积中的任意一种。
进一步的，所述Si/SiO2衬底为p-(100)晶向、厚度为300nm。
进一步的，所述凹槽图形为圆孔图形阵列。
进一步的，所述高纯度硫粉的纯度为99.999％，所述高纯度锗粉的纯度为99.999％。
进一步的，所述将所述处理后的衬底放进化学气相沉积设备中进行生长，生长源为高纯度硫粉和高纯度锗粉，从而制得SiO2衬底上的硫化锗单晶薄膜，具体包括：
将所述处理后的衬底放进化学气相沉积设备中生长；
将所述处理后的衬底倒扣在石英支架上，下方为盛放锗粉的氧化铝坩埚；
盛放硫粉的坩埚放置在气路上游；
经过一定时间的生长，制得SiO2衬底上的硫化锗单晶薄膜。
进一步的，生长过程中的氛围采用硫蒸气或者硫化氢气体。
进一步的，盛放锗粉的氧化铝坩埚的区域的生长温度设置为800℃，升温速率为15℃/min。
进一步的，盛放硫粉的坩埚距离所述处理后的衬底为8cm，该区域温度设置为200℃，升温速率为5℃/min。
本发明相对于现有技术具有如下的有益效果：
1、通过本发明所提供的制备方法，制备的硫化锗单晶薄膜可以直接生长在衬底上，非常有利于和硅基器件单片集成。
2、本发明采用离子增强化学气相沉积设备，可以一次性制备数十片SiO2衬底上的硫化锗单晶薄膜，此外采用等离子增强，促进源的低温裂解，可以降低硫化锗单晶薄膜的生长温度。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图示出的结构获得其他的附图。
图1为本发明实施例的在Si/SiO2衬底上刻蚀图形后的剖视图。
图2为本发明实施例的在图形衬底上蒸镀一层锗晶体层的剖视图。
图3为本发明实施例的衬底在等离子增强化学气相沉积设备中进行生长的示意图。
图4为本发明实施例的在SiO2衬底上生长的硫化锗单晶薄膜的剖视图。
图5为本发明实施例的硫化锗单晶薄膜的XRD衍射图。
图6为本发明实施例的硫化锗单晶薄膜的光致发光谱。
其中：01-Si衬底层、02-SiO2衬底层、03-图形衬底、04-锗晶体种子层、05-PE-CVD示意图、06-硫化锗单晶层。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例，基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。应当理解，描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
实施例：
本实施例提供的在SiO2衬底上生长硫化锗单晶薄膜的制备方法，能够得到在非晶衬底上厚度为1微米左右的高质量硫化锗单晶薄膜。制得的单晶薄膜晶体质量好，表面平整，粗糙度仅为零点几个纳米。经过光致发光谱测试，在蓝紫光波段，波长为410nm和445nm处有两个发光峰，表明具有应用于可见光探测领域的潜力。
本实施例提供的一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法，包括以下步骤：
(1)优选地，衬底为p-(100)晶向，厚度为300nm的Si/SiO2衬底。
(2)用丙酮、乙醇和去离子水对衬底进行表面清洗。
(3)如图1所示，优选地，在衬底上进行光刻，旋涂光刻胶，曝光后显影，刻出直径为50微米的圆孔图形阵列，随后在110℃下烘烤90s，进行坚膜。
(4)优选地，使用电感耦合等离子体刻蚀(ICP，Inductive Coupled PlasmaEmission Spectrometer)刻蚀SiO2层，刻蚀速率为10nm每秒，刻蚀时间为25s，直到刻蚀到下方Si衬底。
(5)如图2所示，优选地，使用电子束蒸发单晶锗颗粒，在刻蚀后的衬底上蒸镀一层20nm的晶体锗，之后清洗掉表面的光刻胶。
(6)如图3所示，优选地，将衬底放进等离子增强化学气相沉积设备(PE-CVD)中进行生长，采用高纯度硫粉(99.999％)和锗粉(99.999％)作为生长源，将衬底倒扣在石英支架上，下方为盛放锗粉的氧化铝坩埚，该区域生长温度设置为800℃，升温速率为15℃/min，盛放硫粉的坩埚放置在气路上游，距离衬底8cm，该区域温度设置为200℃，升温速率为5℃/min。生长过程中的氛围采用硫蒸气或者硫化氢气体；传输气体为氩气，气压为1个大气压，生长温度为800℃下保温生长1h。
图4为在SiO2衬底上生长的硫化锗单晶薄膜；图5为硫化锗单晶薄膜的XRD衍射图；图6为硫化锗单晶薄膜的光致发光谱。由此可见，制得的硫化锗单晶薄膜晶体质量好，表面平整，粗糙度仅为零点几个纳米；经过光致发光谱测试，在蓝紫光波段，波长为410nm和445nm处有两个发光峰，表明具有应用于可见光探测领域的潜力。
综上所述，本发明公开的制备方法包括对衬底进行预处理，在衬底上蒸镀一层Ge晶体作为形核层，以及在化学气相沉积设备(CVD)中高温硫化。采用所述方法可以制备类似绝缘体上应变硅/锗(SOI/GOI)的绝缘体上硫化锗单晶，能够得到在非晶衬底上厚度为1微米左右的高质量硫化锗单晶薄膜。制得的单晶薄膜晶体质量好，表面平整，粗糙度仅为零点几个纳米；经过光致发光谱测试，在蓝紫光波段，波长为410nm和445nm处有两个发光峰，表明具有应用于可见光探测领域的潜力。
以上所述，仅为本发明专利较佳的实施例，但本发明专利的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明专利所公开的范围内，根据本发明专利的技术方案及其发明构思加以等同替换或改变，都属于本发明专利的保护范围。

Claims (10)

1.一种在SiO2衬底上生长硫化锗单晶薄膜的制备方法，其特征在于，所述方法包括：
用丙酮、乙醇和去离子水对衬底进行表面清洗；其中，所述衬底材料为Si/SiO2衬底或SiO2玻璃衬底；
在所述衬底上进行光刻，旋涂光刻胶，进行光刻后再经过干法刻蚀或湿法腐蚀获得凹槽图形；
在所述衬底的凹槽图形中沉积一层锗晶体，得到处理后的衬底；
将所述处理后的衬底放进化学气相沉积设备中进行生长，生长源为高纯度硫粉和高纯度锗粉，从而制得SiO2衬底上的硫化锗单晶薄膜。
2.根据权利要求1所述的制备方法，其特征在于，所述湿法腐蚀包括BOE溶液或食人鱼溶液，所述干法刻蚀包括电感耦合等离子体刻蚀。
3.根据权利要求1所述的制备方法，其特征在于，所述在所述衬底的凹槽图形中沉积一层锗晶体，采用的方法为电子束蒸镀、激光脉冲沉积、物理气相沉积物理溅射、物理气相沉积和化学气相沉积中的任意一种。
4.根据权利要求1所述的制备方法，其特征在于，所述Si/SiO2衬底为p-(100)晶向、厚度为300nm。
5.根据权利要求1所述的制备方法，其特征在于，所述凹槽图形为圆孔图形阵列。
6.根据权利要求1所述的制备方法，其特征在于，所述高纯度硫粉的纯度为99.999％，所述高纯度锗粉的纯度为99.999％。
7.根据权利要求1所述的制备方法，其特征在于，所述将所述处理后的衬底放进化学气相沉积设备中进行生长，生长源为高纯度硫粉和高纯度锗粉，从而制得SiO2衬底上的硫化锗单晶薄膜，具体包括：
将所述处理后的衬底放进化学气相沉积设备中生长；
将所述处理后的衬底倒扣在石英支架上，下方为盛放锗粉的氧化铝坩埚；
盛放硫粉的坩埚放置在气路上游；
经过一定时间的生长，制得SiO2衬底上的硫化锗单晶薄膜。
8.根据权利要求7所述的制备方法，其特征在于，生长过程中的氛围采用硫蒸气或者硫化氢气体。
9.根据权利要求7所述的制备方法，其特征在于，盛放锗粉的氧化铝坩埚的区域的生长温度设置为800℃，升温速率为15℃/min。
10.根据权利要求7所述的制备方法，其特征在于，盛放硫粉的坩埚距离所述处理后的衬底为8cm，该区域温度设置为200℃，升温速率为5℃/min。
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