Nanocellulose Paper Semiconductor with a 3D Network Structure and Its Nano-Micro-Macro Trans-Scale Design

Hirotaka Koga; Kazuki Nagashima; Koichi Suematsu; Tsunaki Takahashi; Luting Zhu; Daiki Fukushima; Yintong Huang; Ryo Nakagawa; Jiangyang Liu; Kojiro Uetani; Masaya Nogi; Takeshi Yanagida; Yuta Nishina

doi:10.1021/acsnano.1c10728

Nanocellulose Paper Semiconductor with a 3D Network Structure and Its Nano-Micro-Macro Trans-Scale Design

ACS Nano. 2022 Jun 28;16(6):8630-8640. doi: 10.1021/acsnano.1c10728. Epub 2022 Apr 26.

Authors

Hirotaka Koga¹, Kazuki Nagashima^{2

3}, Koichi Suematsu⁴, Tsunaki Takahashi^{2

3}, Luting Zhu¹, Daiki Fukushima¹, Yintong Huang¹, Ryo Nakagawa⁵, Jiangyang Liu², Kojiro Uetani¹, Masaya Nogi¹, Takeshi Yanagida^{2

6}, Yuta Nishina⁷

Affiliations

¹ SANKEN (The Institute of Scientific and Industrial Research), Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan.
² Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
³ Japan Science and Technology Agency (JST), PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan.
⁴ Department of Advanced Materials Science and Engineering, Faculty of Engineering Sciences, Kyushu University, 6-1 Kasuga-Koen, Kasuga, Fukuoka 816-8580, Japan.
⁵ Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.
⁶ Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-Koen, Kasuga, Fukuoka 816-8580, Japan.
⁷ Research Core for Interdisciplinary Sciences, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.

Abstract

Semiconducting nanomaterials with 3D network structures exhibit various fascinating properties such as electrical conduction, high permeability, and large surface areas, which are beneficial for adsorption, separation, and sensing applications. However, research on these materials is substantially restricted by the limited trans-scalability of their structural design and tunability of electrical conductivity. To overcome this challenge, a pyrolyzed cellulose nanofiber paper (CNP) semiconductor with a 3D network structure is proposed. Its nano-micro-macro trans-scale structural design is achieved by a combination of iodine-mediated morphology-retaining pyrolysis with spatially controlled drying of a cellulose nanofiber dispersion and paper-crafting techniques, such as microembossing, origami, and kirigami. The electrical conduction of this semiconductor is widely and systematically tuned, via the temperature-controlled progressive pyrolysis of CNP, from insulating (10¹² Ω cm) to quasimetallic (10^-2 Ω cm), which considerably exceeds that attained in other previously reported nanomaterials with 3D networks. The pyrolyzed CNP semiconductor provides not only the tailorable functionality for applications ranging from water-vapor-selective sensors to enzymatic biofuel cell electrodes but also the designability of macroscopic device configurations for stretchable and wearable applications. This study provides a pathway to realize structurally and functionally designable semiconducting nanomaterials and all-nanocellulose semiconducting technology for diverse electronics.

Keywords: customized 3D network structures; nanocellulose; paper electronics; semiconductor; trans-scale structural design; tunable electrical property.