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Unique Three-Dimensional InP Nanopore Arrays for Improved Photoelectrochemical Hydrogen Production Qiang Li,† Maojun Zheng,*,†,‡ Liguo Ma,† Miao Zhong,§ Changqing Zhu,† Bin Zhang,† Faze Wang,† Jingnan Song,† Li Ma,∥ and Wenzhong Shen† †
Key Laboratory of Artificial Structure and Quantum Control, Ministry of Education, Department of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai, 200240, People’s Republic of China ‡ Collaborative Innovation Center of Advanced Microstructures, Nanjing 210093, People’s Republic of China § Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan ∥ School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, Shanghai 200240, People’s Republic of China S Supporting Information *
ABSTRACT: Ordered three-dimensional (3D) nanostructure arrays hold promise for high-performance energy harvesting and storage devices. Here, we report the fabrication of InP nanopore arrays (NPs) in unique 3D architectures with excellent light trapping characteristic and large surface areas for use as highly active photoelectrodes in photoelectrochemical (PEC) hydrogen evolution devices. The ordered 3D NPs were scalably synthesized by a facile two-step etching process of (1) anodic etching of InP in neutral 3 M NaCl electrolytes to realize nanoporous structures and (2) wet chemical etching in HCl/H3PO4 (volume ratio of 1:3) solutions for removing the remaining top irregular layer. Importantly, we demonstrated that the use of neutral electrolyte of NaCl instead of other solutions, such as HCl, in anodic etching of InP can significantly passivate the surface states of 3D NPs. As a result, the maximum photoconversion efficiency obtained with ∼15.7 μm thick 3D NPs was 0.95%, which was 7.3 and 1.4 times higher than that of planar and 2D NPs. Electrochemical impedance spectroscopy and photoluminescence analyses further clarified that the improved PEC performance was attributed to the enhanced charge transfer across 3D NPs/electrolyte interfaces, the improved charge separation at 3D NPs/electrolyte junction, and the increased PEC active surface areas with our unique 3D NP arrays. KEYWORDS: photoelectrochemical cells, InP, three-dimensional, nanopore arrays, anodic etching
1. INTRODUCTION
enhanced surface areas for improved electrochemical reactions.5,17 To achieve high-efficiency PEC hydrogen production, the use of semiconductors that are capable of absorbing a broad spectrum of solar light is desirable. However, most of the metal oxide semiconductors such as TiO2 and ZnO can only absorb light in the ultraviolet (UV) region due to their relatively large band gap (Eg = 3.2 eV). The narrow band gap metal oxide of αFe2O3 is able to absorb visible light up to 600 nm; however, it suffers from low absorption coefficient and short carrier diffusion length, and therefore poor incident-phototocurrent efficiency (IPCE;
