Facile Semiconductor p-n Homojunction Nanowires with Strategic p-Type Doping Engineering Combined with Surface Reconstruction for Biosensing Applications

doi:10.1007/s40820-024-01394-5

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Abstract

Photosensors with versatile functionalities have emerged as a cornerstone for breakthroughs in the future optoelectronic systems across a wide range of applications. In particular, emerging photoelectrochemical (PEC)-type devices have recently attracted extensive interest in liquid-based biosensing applications due to their natural electrolyte-assisted operating characteristics. Herein, a PEC-type photosensor was carefully designed and constructed by employing gallium nitride (GaN) p-n homojunction semiconductor nanowires on silicon, with the p-GaN segment strategically doped and then decorated with cobalt-nickel oxide (CoNiO_x). Essentially, the p-n homojunction configuration with facile p-doping engineering improves carrier separation efficiency and facilitates carrier transfer to the nanowire surface, while CoNiO_x decoration further boosts PEC reaction activity and carrier dynamics at the nanowire/electrolyte interface. Consequently, the constructed photosensor achieves a high responsivity of 247.8 mA W⁻¹ while simultaneously exhibiting excellent operating stability. Strikingly, based on the remarkable stability and high responsivity of the device, a glucose sensing system was established with a demonstration of glucose level determination in real human serum. This work offers a feasible and universal approach in the pursuit of high-performance bio-related sensing applications via a rational design of PEC devices in the form of nanostructured architecture with strategic doping engineering.

Key words： p-n GaN nanowires Strategic p-doping Surface decoration Photoelectrochemical sensor Glucose sensing

Received: 31 January 2024 Published: 14 May 2024

Corresponding Authors: Zongzhi Yin, Haiding Sun

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Liuan Li and Shi Fang contributed equally to this work.

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	Liuan Li
	Shi Fang
	Wei Chen
	Yueyue Li
	Mohammad Fazel Vafadar
	Danhao Wang
	Yang Kang
	Xin Liu
	Yuanmin Luo
	Kun Liang
	Yiping Dang
	Lei Zhao
	Songrui Zhao
	Zongzhi Yin
	Haiding Sun

Cite this article:

Liuan Li,Shi Fang,Wei Chen, et al. Facile Semiconductor p-n Homojunction Nanowires with Strategic p-Type Doping Engineering Combined with Surface Reconstruction for Biosensing Applications[J]. Nano-Micro Letters, 2024, 16(1): 192-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01394-5 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/192

Fig. 1 Band structure design of GaN nanowire. Schematic of a n-GaN nanowire and b p-n GaN nanowire structure. Band diagrams of c n-GaN and d p-n GaN nanowire in contact with the electrolytes under illumination. The EFn and EFp are the electron and hole quasi-Fermi levels, respectively. The Vph represents the photovoltage generated in the nanowires. e Comparison of photovoltages of n-GaN and p-n GaN nanowires. Data are extracted from Fig. S1c. f Relationship between the p-GaN segment surface band bending and the resulting photocurrent

Fig. 2 Surface band characterization and investigation of the charge transfer properties. a Mott-Schottky plots measured under dark conditions. b Surface potential measured by KPFM shows the average CPD values, and XPS valence spectra show the relative location of the valence band maximum to the Fermi level. c EIS plots measured at 340 nm with a light intensity of 0.1 mW cm−2 (0 V vs. Ag/AgCl). d The Rct, Rbulk, and Rs fitted values extracted from EIS plots (measured under different applied biases). e Photocurrents measured at 340 nm with light intensity of 0.1 mW cm−2. f SPV measured by KPFM under 340-nm irradiation

Fig. 3 Surface modification and material characterizations. a Schematics of the carrier dynamics of the pristine GaN and surface-modified GaN nanowires. b 30°-tilted and top-view SEM images of the p-n GaN/CoNiOx nanowires. c TEM image of the p-n GaN/CoNiOx nanowires. d The enlarged image of the blue-outlined area in (c). e Corresponding EDS elemental mapping of the p-n GaN/CoNiOx nanowires. XPS spectra for f Co 2p and g Ni 2p of p-n GaN/CoNiOx nanowires

Fig. 4 Investigation of photogenerated carrier dynamics and evaluation of photoresponse. a TRPL curves of the p-n GaN and p-n GaN/CoNiOx nanowires. b Open-circuit potential measurements at 340 nm with a light intensity of 0.1 mW cm−2. c SPV measured under 340-nm irradiation. d Photocurrents measured at 340 nm with a light intensity of 0.1 mW cm−2. e Comparison of the spectral response of the p-n GaN and p-n GaN/CoNiOx photoelectrodes. f Responsivity and photocurrent density of the p-n GaN/CoNiOx photoelectrode at 340 nm with various light intensities. g Continuous on/off cycle test (27.5 h) of the p-n GaN/CoNiOx photoelectrode. h Comparison of the responsivity and stability of previously reported PEC-type photosensors and this work

Table 1

Comparison of the performance of various self-powered photoelectrochemical photosensors

Fig. 5 Demonstration of PEC glucose sensing using the p-n GaN/CoNiOx photoelectrode. a Schematic mechanism for PEC glucose sensing using the p-n GaN/CoNiOx photoelectrode. b Photocurrent versus time for the p-n GaN/CoNiOx photoelectrode with continuous addition of glucose upon 340-nm chopping illumination. c The linear relationship between the photocurrent and glucose concentration. d Reproducibility tests on five parallel prepared p-n GaN/CoNiOx photoelectrodes under 30-µM glucose. e Stability tests of the p-n GaN/CoNiOx photoelectrode under 30-µM glucose. The photoelectrode was kept in dry conditions and at room temperature. f Effect of interference on the photocurrent by adding fructose, lactose, maltose, urea, and uric acid into the electrolyte

Table 2

Determination of glucose concentration in real (human serum) samples

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