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3D nonlinear photolithography of Tin oxide ceramics via femtosecond laser

氧化锡陶瓷的飞秒激光3D非线性光刻

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Abstract

As a wide band gap semiconductor material, tin oxide (SnO2) has been widely used in gas sensing, optoelectronics and catalysis. The complex micro and nanoscale three-dimensional (3D) geometric structures endow the conventional SnO2 ceramics with novel properties and functionalities. Nevertheless, ceramics cannot be cast or machined easily due to their high mechanical toughness and resistance. The additive manufacturing opens a great opportunity for flexibly geometrical shaping, while the arbitrary shaping of SnO2 ceramics at micro and nanoscale is always a challenge. Herein, preceramic monomers which can be polymerized under ultrafast laser irradiation, were utilized to form complex and arbitrary 3D preceramic polymer structures. After calcination treatment, these green-body structures could be converted into pure high-dense SnO2 ceramics with uniform shrinkage, and the feature size was down to submicron. Transmission electron microscopy (TEM) analysis displays that the printed SnO2 ceramic nanostructures can be nanocrystallized with grain sizes of 2.5 ± 0.4 nm. This work provides the possibility of manufacturing 3D SnO2 ceramic nanostructures arbitrarily with sub-100 nm resolution, thus making it promising for the applications of SnO2 in different fields.

摘要

氧化锡是一种宽带隙半导体材料, 广泛用于气体传感、光电 和催化等领域. 微米级至纳米级的复杂三维几何结构使传统的氧 化锡陶瓷具有新的特性和功能. 由于具有高的机械韧性和强度, 陶 瓷不易铸造或加工. 增材制造为陶瓷材料灵活的几何造型带来了 巨大的机会, 但是极高的熔化温度使其在普通的3D打印方法上更 加困难, 而在微米或纳米尺度任意成形氧化锡陶瓷始终是一个挑 战. 本文中, 我们利用在超快激光辐照下聚合的陶瓷前驱体, 形成 复杂且任意的3D陶瓷聚合物结构, 通过煅烧处理后转变为具有均 匀收缩率的高密度纯氧化锡陶瓷, 特征尺寸可降至亚微米. 透射电 子显微镜(TEM)分析显示, 氧化锡陶瓷纳米晶体的晶粒尺寸为2.5 ± 0.4 nm. 这项工作为制造精度高达亚百纳米的任意3D氧化锡陶瓷 纳米结构提供了可能性, 从而使其在不同领域更具应用前景.

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Acknowledgements

This work was supported by Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory (XHT2020-003 and XHT2020-005), the Fundamental Research Funds for the Central Universities (2020IVA068), the Creative Research Group Project of Natural Science Foundation of China (61821003), and the National Natural Science Foundation of China (61775068 and 51802239).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, 430070, China

    Nianyao Chai  (柴年垚), Yunfan Yue  (岳云帆), Ping Wei  (魏平), Xuewen Wang  (王学文), Junjie Zhao  (赵俊杰), Qi Zhang  (张奇), Fuzhi Huang  (黄福志), Zhongle Zeng  (曾终乐), Liqiang Mai  (麦立强) & Yibing Cheng  (程一兵)

  2. Foshan Xianhu Laboratory of the Advanced Energy Science and Technology, Guangdong Laboratory, Foshan, 528216, China

    Nianyao Chai  (柴年垚), Xuewen Wang  (王学文), Liqiang Mai  (麦立强) & Yibing Cheng  (程一兵)

  3. Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Hubei, 430074, China

    Yanan Liu  (刘亚男) & Zongsong Gan  (甘棕松)

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  1. Nianyao Chai  (柴年垚)
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  2. Yanan Liu  (刘亚男)
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  9. Zhongle Zeng  (曾终乐)
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  10. Zongsong Gan  (甘棕松)
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Contributions

Cheng Y and Mai L were in charge of this scientific research project; Wang X and Gan Z finalized the manuscript; Chai N and Liu Y conducted most of the experiments and data analyses together as well as wrote the manuscript; Zhang Q and Huang F contributed to the photoresit preparation and analysis; Zeng Z and Wei P performed the HRTEM analysis and helped discuss and revise the manuscript; Yue Y and Zhao J performed the pyrolysis experiments and contributed to revising the manuscript. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Corresponding authors

Correspondence to Xuewen Wang  (王学文), Zongsong Gan  (甘棕松) or Liqiang Mai  (麦立强).

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Supporting data are available in the online version of the paper.

Nianyao Chai received his BS degree in 2018 from Wuhan University of Technology (WUT). He is currently a PhD candidate at WUT. His current research interest is focused on the field of ultrafast laser 3D nonlinear photolithography.

Yanan Liu received her Master degree in 2017 from Hebei University in China, and is currently a PhD candidate at Huazhong University of Science and Technology. Her research direction is laser direct writing crystallization technology of optical materials.

Xuewen Wang obtained his PhD degree in 2017 from Swinburne University of Technology, and joined WUT in 2019, and acted as the deputy director of the Femtosecond Laser Manufacturing Center for Advanced Materials and Devices. His research interests include the ultrafast lasermatter interactions, laser-derived nanomaterial synthesis and modification, ceramic nanostructuring, and nonlinear photolithography.

Zongsong Gan received his BS degree in 2008 from Nankai University, China, and PhD degree in 2013 from Swinburne University of Technology, Australia. Now he is a professor of Wuhan Optoelectronics National Research Center, Huazhong University of Science and Technology. His research direction is the development of new principle lithography machine technology and new photoresist materials.

Liqiang Mai, Chair Professor of Materials Science and Engineering at WUT, Dean of School of Materials Science and Engineering at WUT, Fellow of the Royal Society of Chemistry. He received his PhD degree in 2004 from WUT and carried out his postdoctoral research at Georgia Institute of Technology in 2006–2007. He worked as an advanced research scholar at Harvard University and the University of California, Berkeley. His current research interests focus on new nanomaterials for electrochemical energy storage and micro/nano energy devices.

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Chai, N., Liu, Y., Yue, Y. et al. 3D nonlinear photolithography of Tin oxide ceramics via femtosecond laser. Sci. China Mater. 64, 1477–1484 (2021). https://doi.org/10.1007/s40843-020-1543-x

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