电催化金属辅助化学刻蚀法制备硅纳米线/多孔硅复合结构

doi:10.15541/jim20200509

无机材料学报 ›› 2021, Vol. 36 ›› Issue (6): 608-614.DOI: 10.15541/jim20200509 CSTR: 32189.14.10.15541/jim20200509

电催化金属辅助化学刻蚀法制备硅纳米线/多孔硅复合结构

陈力驰¹^,²(), 王耀功¹^,², 王文江¹^,², 麻晓琴¹^,², 杨静远³(), 张小宁¹^,²

1.西安交通大学电子物理与器件教育部重点实验室, 西安 710049
2.西安交通大学电子科学与工程学院, 西安 710049
3.生态环境部核与辐射安全中心, 北京 100082

收稿日期:2020-09-01 修回日期:2020-10-12 出版日期:2021-06-20 网络出版日期:2020-12-01
通讯作者: 杨静远, 工程师. E-mail: yjytonghu@163.com
作者简介:陈力驰(1995-), 男, 博士研究生. E-mail: 734167430@qq.com
基金资助:
国家自然科学基金(51807156);国家自然科学基金(61771382);陕西省国际合作计划项目(2018KW-034);陕西省博士后基金(2018BSHYDZZ22)

Preparation of Silicon Nanowires and Porous Silicon Composite Structure by Electrocatalytic Metal Assisted Chemical Etching

CHEN Lichi¹^,²(), WANG Yaogong¹^,², WANG Wenjiang¹^,², MA Xiaoqin¹^,², YANG Jingyuan³(), ZHANG Xiaoning¹^,²

1. Key Laboratory of Physical Electronics and Devices of the Ministry of Education, Xi’an Jiaotong University, Xi’an 710049, China
2. School of Electronic Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, China
3. Nuclear and Radiation Safety Center, Beijing 100082, China

Received:2020-09-01 Revised:2020-10-12 Published:2021-06-20 Online:2020-12-01
Contact: YANG Jingyuan, engineer. E-mail: yjytonghu@163.com
About author:CHEN Lichi(1995-), male, PhD candidate. E-mail: 734167430@qq.com
Supported by:
National Natural Science Foundation of China(51807156);National Natural Science Foundation of China(61771382);International Cooperation Project of Shaanxi Province(2018KW-034);Shaanxi Province Postdoctoral Science Foundation(2018BSHYDZZ22)

摘要/Abstract

摘要：

量子限制效应使硅纳米线具有良好的场致发射特性, 结合多孔硅的准弹道电子漂移模型可提高场发射器件的性能。传统的金属辅助化学刻蚀法制备硅纳米线的效率较低, 本研究在传统方法的基础上引入恒流源, 提出电催化金属辅助化学刻蚀法, 高效制备了硅纳米线/多孔硅复合结构。在外加30 mA恒定电流的条件下, 硅纳米线的平均制备速率可达308 nm/min, 较传统方法提升了173%。研究了AgNO₃浓度、刻蚀时间和刻蚀电流对复合结构形貌的影响规律; 测试了采用电催化金属辅助化学刻蚀法制备样品的场发射特性。结果显示样品的阈值场强为10.83 V/μm, 当场强为14.16 V/μm时, 电流密度为64 μA/cm²。

关键词: 电化学, 金属辅助化学刻蚀法, 硅纳米线, 多孔硅, 场发射

Abstract:

The quantum confinement effect brings good field emission characteristics to silicon nanowires, which is expected to improve the performance of field emission device through combination with the quasiballistic electrons drift model in porous silicon structure, but the efficiency of traditional metal assisted chemical etching is low. Constant current source was introduced on the basis of traditional metal assisted chemical etching in the present work, and a electrocatalytic metal assisted chemical etching method was proposed to achieve high-efficiency preparation of silicon nanowires and porous silicon composite structure. The preparation rate of silicon nanowires is 308 nm/min at 30 mA current, which is increased by 173% compared with that adopted the traditional method. Moreover, the effects of AgNO₃ concentration, etching time and etching current on the morphology of the composite structure were investigated. The field emission characteristics of the structure prepared by electrocatalytic metal assisted chemical etching were tested. The current density is 64 μA/cm² under the electric field of 14.16 V/μm, and threshold electric field is 10.83 V/μm.

Key words: electrochemistry, metal assisted chemical etching, silicon nanowire, porous silicon, field emission

中图分类号:

TQ150

陈力驰, 王耀功, 王文江, 麻晓琴, 杨静远, 张小宁. 电催化金属辅助化学刻蚀法制备硅纳米线/多孔硅复合结构[J]. 无机材料学报, 2021, 36(6): 608-614.

CHEN Lichi, WANG Yaogong, WANG Wenjiang, MA Xiaoqin, YANG Jingyuan, ZHANG Xiaoning. Preparation of Silicon Nanowires and Porous Silicon Composite Structure by Electrocatalytic Metal Assisted Chemical Etching[J]. Journal of Inorganic Materials, 2021, 36(6): 608-614.

图/表 9

图1 制备装置示意图

Fig. 1 Schematic drawing of preparation device

图2 采用不同方法制备样品的SEM照片

Fig. 2 SEM morphologies of samples prepared by different methods (a,d) EMACE 2-step method; (b,e) MACE 2-step method; (c) EMACE 1-step method; (f) High resolusion FESEM images of SiNWs clusters; (g) EDS of SiNWs clusters

图3 AgNO3浓度对SiNWs/PS复合结构形貌的影响

Fig. 3 Effect of AgNO3 concentration on the morphology of SiNWs/PS composites (a) Changes of length of SiNWs, PS and cluster with AgNO3 concentration, and FESEM images of SiNWs/PS composites with AgNO3 concentration of (b) 1 mmol/L and (c) 20 mmol/L

图4 刻蚀时间对SiNWs/PS复合结构形貌的影响

Fig. 4 Effect of etching time on the morphology of SiNWs/PS composites (a) Changes of length of SiNWs, PS and cluster with etching time, and FESEM images of SiNWs/PS composites with etching time of (b) 1 min and (c) 20 min

图5 刻蚀电流对SiNWs/PS复合结构形貌的影响

Fig. 5 Effect of etching current on the morphology of SiNWs/PS composites

图6 采用不同电流值制备样片的SEM照片

Fig. 6 Comparison of the morphology of samples prepared by different currents at the same scale (a) Cross section; (b) Surface

图7 EMACE法原理示意图

Fig. 7 Schematic diagram of EMACE method

图8 刻蚀过程中阴阳极间的电压/电流随时间的变化

Fig. 8 Variation of voltage/current between anode and cathode with time during the etching (a) EMACE 2-step method at 10 mA; (b) EMACE 2-step method at 30 mA; (c) EMACE 1-step method at 10 mA

图9 场发射特性测试结果

Fig. 9 Test results of field emission characteristics (a) J-E curves; (b) Repeatability test

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电催化金属辅助化学刻蚀法制备硅纳米线/多孔硅复合结构

Preparation of Silicon Nanowires and Porous Silicon Composite Structure by Electrocatalytic Metal Assisted Chemical Etching

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