氮掺杂p型ZnO薄膜制备及相关问题研究
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摘要
氧化锌(ZnO)是一种直接宽带隙半导体材料,其室温下带隙宽度为3.37eV，且激子束缚能高达60meV，在室温甚至更高温度下都可获得高效的紫外激子发光。自从1997年ZnO薄膜在室温光泵紫外受激发射被香港和日本的科学家首次实现以来，ZnO材料研究迅速成为国际光电子领域前沿课题中的研究热点。然而，在ZnO的器件化道路上，仍然面临许多需要解决的困难。我们针对以下几方面的问题开展研究：(1)异质结构是光电器件不可缺少的组成部分。高平整度的ZnO外延薄膜是实
现界面陡峭异质结构的前提。但由于低温掺杂的限制，低温生长的平整度
难以达到量子阱等异质结构的要求，非常有必要进行低温高质量的ZnO薄
膜的生长的探索。(2)可重复、高质量、低电阻的p型ZnO薄膜是实现光电子器件应用的必要前
提。但是到目前为止，虽然有不少关于p型ZnO的报道，但p型ZnO薄
膜的低迁移率和低空穴浓度一直是阻碍ZnO在光电子学领域继续发展的主
要瓶颈，需要尝试新的掺杂方式提高p型ZnO的电学性质。
本论文针对以上问题进行研究，取得的主要结果如下：(1)利用P-MBE设备，通过改变Zn/O比例，控制Zn源流量，改变生长模式，
控制生长速度，在低温下实现高质量外延薄膜的生长，得到原子级平整的
ZnO薄膜。(2)利用P-MBE设备,通过射频等离子体源激活NO气体使其成为活化的掺杂
N源和生长O源，获得了N掺杂的p型ZnO薄膜。通过在生长过程中间歇性补氧，获得了较为稳定的p型电导。(3)通过等离子体溅射出B原子实现B-N共掺，提高N受主在ZnO中的掺入量，提高了N掺杂p型ZnO的重复率。Hall测试结果显示空穴载流子浓度达到8.6×1018cm-3，霍尔迁移率为2.13cm2/Vs。在长达两年的放置期间一直表现稳定的p型电导。
Zinc oxide (ZnO) is a direct wide band gap semiconductor material. The bandgapof3.37eV and the exciton binding energy as high as60meV at room temperature (RT)assure the efficient UV exciton emition at room temperature or even highertemperature. Since the light pumped lasing of ZnO was realized for the first time in1997by the scientists from Japan and Hong Kong at room temperature, the ZnOmaterials become the frontier topics fast in the field of international optoelectronicsresearch. However, In order to realize the devices of ZnO, there are still someproblems need to be resolved, The problems as follows were researched in thisdissertation:
(1) Heterostructure is an integral part of the photoelectric device. The premise torealize the steep heterostructure of interface is obtained the smooth surfaceepitaxial ZnO thin film. But the limitation of doping at low temperature, thesmoothness of the ZnO thin films growth at low temperature is difficult to meetthe requirements of quantum-well heterostructure.
(2) The necessary premise to realize the optoelectronic devices is obtained arepeatable, high quality and low resistivity p-type ZnO thin film, but so far,many researchers reported the p-type ZnO, but the low mobility and lowconcentration of holes of p-type ZnO thin film have been hampering thecontinue development for ZnO in the field of optoelectronics.
In order to solve above problems of ZnO, in this paper, we obtained main conclusionsas follows:
(1) We used P-MBE equipment, by changing the Zinc/O ratio, controlled Zincsource flow, controlled the growth speed, the growth mode was changed, we obtained high quality epitaxial thin films at low growth temperature, ZnO thinfilms have the atomic smooth surface.
(2) NO gas (99.999%) was used as oxygen source and nitrogen source, which wasactivated by rf plasma, N doped p-type ZnO thin films were obtained. And thestability of p-type conductivity was improved through intermittent oxygensupplement in the growth process.
(3) Boron was introduced into the chamber by plasma bombarding the boron nitridedischarge tube, B-N codoped ZnO was obtained. The N acceptors concentrationwas increased, and N doped p-type ZnO repetition rate was improved. Halleffect test shows that the holes concentration reaches8.6×1018cm-3, Hallmobility is2.13cm2/Vs, and it displays a stable p-type conductivity during thetwo years preservation period.
现界面陡峭异质结构的前提。但由于低温掺杂的限制，低温生长的平整度
难以达到量子阱等异质结构的要求，非常有必要进行低温高质量的ZnO薄
膜的生长的探索。(2)可重复、高质量、低电阻的p型ZnO薄膜是实现光电子器件应用的必要前
提。但是到目前为止，虽然有不少关于p型ZnO的报道，但p型ZnO薄
膜的低迁移率和低空穴浓度一直是阻碍ZnO在光电子学领域继续发展的主
要瓶颈，需要尝试新的掺杂方式提高p型ZnO的电学性质。
本论文针对以上问题进行研究，取得的主要结果如下：(1)利用P-MBE设备，通过改变Zn/O比例，控制Zn源流量，改变生长模式，
控制生长速度，在低温下实现高质量外延薄膜的生长，得到原子级平整的
ZnO薄膜。(2)利用P-MBE设备,通过射频等离子体源激活NO气体使其成为活化的掺杂
N源和生长O源，获得了N掺杂的p型ZnO薄膜。通过在生长过程中间歇性补氧，获得了较为稳定的p型电导。(3)通过等离子体溅射出B原子实现B-N共掺，提高N受主在ZnO中的掺入量，提高了N掺杂p型ZnO的重复率。Hall测试结果显示空穴载流子浓度达到8.6×1018cm-3，霍尔迁移率为2.13cm2/Vs。在长达两年的放置期间一直表现稳定的p型电导。
Zinc oxide (ZnO) is a direct wide band gap semiconductor material. The bandgapof3.37eV and the exciton binding energy as high as60meV at room temperature (RT)assure the efficient UV exciton emition at room temperature or even highertemperature. Since the light pumped lasing of ZnO was realized for the first time in1997by the scientists from Japan and Hong Kong at room temperature, the ZnOmaterials become the frontier topics fast in the field of international optoelectronicsresearch. However, In order to realize the devices of ZnO, there are still someproblems need to be resolved, The problems as follows were researched in thisdissertation:
(1) Heterostructure is an integral part of the photoelectric device. The premise torealize the steep heterostructure of interface is obtained the smooth surfaceepitaxial ZnO thin film. But the limitation of doping at low temperature, thesmoothness of the ZnO thin films growth at low temperature is difficult to meetthe requirements of quantum-well heterostructure.
(2) The necessary premise to realize the optoelectronic devices is obtained arepeatable, high quality and low resistivity p-type ZnO thin film, but so far,many researchers reported the p-type ZnO, but the low mobility and lowconcentration of holes of p-type ZnO thin film have been hampering thecontinue development for ZnO in the field of optoelectronics.
In order to solve above problems of ZnO, in this paper, we obtained main conclusionsas follows:
(1) We used P-MBE equipment, by changing the Zinc/O ratio, controlled Zincsource flow, controlled the growth speed, the growth mode was changed, we obtained high quality epitaxial thin films at low growth temperature, ZnO thinfilms have the atomic smooth surface.
(2) NO gas (99.999%) was used as oxygen source and nitrogen source, which wasactivated by rf plasma, N doped p-type ZnO thin films were obtained. And thestability of p-type conductivity was improved through intermittent oxygensupplement in the growth process.
(3) Boron was introduced into the chamber by plasma bombarding the boron nitridedischarge tube, B-N codoped ZnO was obtained. The N acceptors concentrationwas increased, and N doped p-type ZnO repetition rate was improved. Halleffect test shows that the holes concentration reaches8.6×1018cm-3, Hallmobility is2.13cm2/Vs, and it displays a stable p-type conductivity during thetwo years preservation period.
引文
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