Enhanced photoelectrochemical properties of copper-assisted catalyzed etching black silicon by electrodepositing cobalt

Black silicon (Si) photoelectrodes are promising for improving the performance of photoelectrochemical (PEC) water splitting. Here, we report the fabrication of p-black Si and n+p-black Si photocathodes via a controllable copper-assisted catalyzed etching method. The etching process affects only the topmost less than 200 nm of Si and is independent of the surface doping. The synergistic effects of the excellent light harvesting of the black Si and the improved charge transfer properties of the p-n junction boost the production and utilization of photogenerated carriers. The mean reflectance of the pristine Si samples is about 10% from 400 to 950 nm, while that of the black Si samples is reduced as low as 5%. In addition, the PEC properties of the n+p-black Si photocathode can be further enhanced by depositing a cobalt (Co) layer. Compared with the p-Si sample, the onset potential of the Co/n+p-black Si photocathode is positively shifted by 560 mV to 0.33 V vs. reversible hydrogen electrode and the saturation photocurrent density is increased from 22.7 to 32.6 mA/cm2. The design of the Co/n+p-black Si photocathode offers an efficient strategy for preparing PEC solar energy conversion devices.