Highly sensitive and selective H2O2 sensors based on ZnO TFT using PBNCs/Pt-NPs/TNTAs as gate electrode

https://doi.org/10.1016/j.snb.2021.130791Get rights and content

Highlights

  • H2O2 sensor based on ZnO thin-film transistors was proposed using PBNCs/Pt-NPs/TNTAs electrode.

  • Detection limit is three orders of magnitude lower than conventional electrochemical methods under the equivalent conditions.

  • The long-term stability has been demonstrated by the constant results from day 1 to day 27.

  • A low detection limit of 5.19 nM and a wide linear detection range were obtained.

  • Inherent amplification of the transistor helps construct highly sensitive and selective H2O2 sensors.

Abstract

A highly sensitive and selective sensor is urgently needed in many practical H2O2 detection, such as water quality monitoring, quality control of food products, and so on. However, the traditional three electrode system limits its further development in recent years due to its difficulty in miniaturization and integration. To effectively improve its sensitivity and selectivity, highly-ordered TiO2 nanotube arrays (TNTAs) are modified with Pt nanoparticles and Prussian blue (PB) nanotubes and creatively combines with thin-film transistor (TFT) based on ZnO to prepare an electrochemical sensor. The sensor uses PBNCs as recognition units for the specific detection of H2O2, and the generated electrical signal is amplified by TFT. Thus, a highly sensitive and selective H2O2 sensor is achieved. The detection limit of the sensor is as low as 5.19 nM, which is three orders of magnitude lower than the conventional electrochemical detection methods using the same electrode. The sensor also possesses wider linear detection range of 0.1–50 μM and 50 μM–5 mM comparable to that of other reported H2O2 sensors. Besides, the sensor has good selectivity for H2O2 in the presence of common interferences such as ascorbic acid, uric acid, glucose, and dopamine. Furthermore, the device presents good reproducibility and exhibits good long-term stability over 27 days of continuous measurement. This study offers important insights for the rational design of sensors with high sensitivity and selectivity.

Introduction

Hydrogen peroxide (H2O2) is a byproduct of enzymatic reactions in many foods and human blood, which plays an important role in cell signaling, host defense, protein folding and oxidative biosynthesis reactions [1]. In addition, H2O2 is a clean and versatile oxidant that has been widely used in environmental, medical, biological and food applications [2], [3], [4], [5], [6]. Therefore, the trace H2O2 in the troposphere has an indirect influence on the process of acid rain formation [7]. However, high H2O2 concentration can corrode the skin, harm human organs and the central nervous system, and even cause cancer [8], [9], [10], [11], [12], which is classified as a carcinogen by the World Health Organization [13]. Therefore, it is necessary to find a rapid, sensitive and accurate detection method to monitor the concentration of H2O2.

Various methods have been developed to detect H2O2, such as chemiluminescence [14], titrimetry [15] and fluorometry [16]. However, these methods have some disadvantages such as complex detection conditions, time-consuming, expensive equipment, and tedious pre-treatment process. Recently, electrochemical methods have attracted the attention of researchers due to its low cost and fast detection speed [17], [18]. In recent years, peroxidases [19], metal oxides [20], [21], carbon nanomaterials [22], noble metal nanoparticles (NPs) [23], [24] and their composites have often been used to fabricate H2O2 electrochemical sensors. Among them, noble metal nanoparticles have the advantages of smaller size, larger specific surface area [25], better catalytic activity [26] and electrical conductivity [27] compared to flake noble metals, which enable them to act as the carrier for biosensitive molecules and improve the stability [28], [29]. Furthermore, many researches have shown that noble metal nanoparticle-based electrochemical sensors can significantly amplify the output signal and have higher sensitivity [28]. Besides, titanium dioxide nanotube arrays (TNTAs) possess highly ordered porous structure, which is suitable as support materials for compositing with noble metal nanoparticles. In addition, this composite material greatly reduces the dependence on noble metals due to their cheap and good biocompatibility, chemical stability, large number of chemically reactive sites, and large specific surface area [30], [31], [32]. In addition, Prussian blue nanocubes (PBNCs) are a kind of artificial peroxidase that possess a selective catalytic capacity to H2O2. However, PBNCs are prone to hydrolysis under neutral or alkaline conditions [33]. Moreover, these H2O2 sensors are using the traditional three-electrode system to collect electrical signals, which are difficult to miniaturize and to integrate for real-time detection. They are insensitive to small changes in electrical signals and lack of stability.

Thin-film transistor (TFT) based biosensors are considered as a promising option for biomolecule detection due to their high sensitivity, low power consumption, inherent signal amplification, miniaturization, and system integration [34]. For example, David et al. [35]. first reported an electrochemical sensor based on PEDOT:PSS, where the source, drain and gate of the device are constructed by PEDOT:PSS. Our previous work, used PEDOT:PSS and TNTAs as the active layer and the gate electrode, respectively [36]. And make the electrode be separated from the TFT. This method makes it easy to replace the gate electrode and also avoid the pollution of the active layer, reducing the fabrication cost. However, the carrier mobility of organic semiconductor is low, and the stability of the sensor can be easily affected by the ion doping in the buffer solution. Recently, metal oxide semiconductors such as ZnO have attracted more attention in biosensors due to their high carrier mobility, small subthreshold swing (SS) and good film uniformity [37], [38].

In this work, we constructed an electrochemical H2O2 sensor based on ZnO TFT using PBNCs/Pt-NPs/TNTAs as the gate electrode. The inherent signal amplification in TFT based sensor can significantly reduce detection limits, extend the detection linearity range, and improve detection performance. The sensor shows a low detection limit down to 5.19 nM for H2O2, which is well below the detection limit of conventional three-electrode electrochemical measurements under equivalent conditions (16.53 μM) and sufficient to characterize H2O2 levels in most biological systems. Besides, the sensor has a wide linear detection range (0.1–50 μM and 50 μM–5 mM) and excellent reproducibility as well as long-term stability. The long-term stability is demonstrated by 27 days of continuous measurements.

Section snippets

Materials and apparatus

Titanium mesh (> 99% purity, 100 meshes) was purchased from Kangwei, China. ZnO Target was purchased from Deyang ONA new materials Co., Ltd. Hydrogen peroxide (H2O2) was obtained from Xilong Scientific Co., Ltd. (Guangdong, China). Dopamine hydrochloride, ascorbic acid (AA), glucose, and uric acid (UA) were obtained from Aladdin Reagent Database Inc. All other chemicals were analytical grade. The ultra-pure water was used to prepare solutions. The phosphate buffer solutions (PBS, pH 6.2) was

Characteristics of the electrodes

The morphology of the Pt-NPs/TNTAs electrode was characterized by FESEM and TEM. Fig. 2a and b shows the surface morphology of the bare TNTAs electrode. It can be seen that the TiO2 nanotubes arrays are highly ordered and vertically arranged. The average diameter of each nanotube is about 80 nm while the length is 8 µm. Fig. S1 shows the XRD pattern of the bare TNTA electrode annealed at 450 ℃, where only anatase diffraction peaks could be observed (JCPDS Card No. 21-1272) [37]. Fig. 2c and d

Conclusions

In summary, a highly sensitive and selective H2O2 sensor was constructed by combining ZnO-based TFT with the prepared PBNCs/Pt-NPs/TNTAs gate electrode materials. The sensor, which used a ZnO-TFT structure to amplify sensing signal, demonstrated as a high performance platform for H2O2 sensing. The ZnO-TFT were prepared by RF magnetron sputtering. As for the electrode material, TNTAs with large surface area were prepared by anodic oxidation as the substrate material to carry Pt-NPs and PBNCs.

CRediT authorship contribution statement

Zui Tao: Investigation, Visualization, Writing – original draft. Hewei Si: Investigation, Writing – review & editing. Xidong Zhang: Formal analysis. Jianjun Liao: Validation. Shiwei Lin: Conceptualization, Supervision.

Declaration of Competing Interest

The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Shiwei Lin reports financial support was provided by National Natural Science Foundation of China.

Acknowledgments

T. Z. and H. S. contributed equally to this work. This work was supported by the National Natural Science Foundation of China (Grant Nos. 61764003 and 21866012), Major Science and Technology Planning Project of Hainan Province (ZDKJ201810), Key Research and Development Program of Hainan Province (ZDYF2020222), and Hainan Academician Innovation Platform Funding.

Zui Tao is a Master candidate in School of Materials Science and Engineering, Hainan University, Haikou, China. He received his Bachelor’s degree in Materials Science and Engineering from Hainan University in 2018. He is currently working on the electrochemical sensors.

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    Zui Tao is a Master candidate in School of Materials Science and Engineering, Hainan University, Haikou, China. He received his Bachelor’s degree in Materials Science and Engineering from Hainan University in 2018. He is currently working on the electrochemical sensors.

    Hewei Si is a PhD candidate in School of Materials Science and Engineering, Hainan University, Haikou, China. She received her Master degree in Materials Science and Engineering from Hainan University in 2019. She is currently working on the photoelectrochemical sensors.

    Xidong Zhang received his Master degree in Materials Science and Engineering from Hainan University in 2020. He currently focuses on research and development of semiconductor-based chemical sensors.

    Jianjun Liao is an associate professor in the School of Ecological and Environmental Sciences at Hainan University, China. He received his PhD degree in Information and Communication Engineering from Hainan University in 2016. His current research interest is nanomaterial-based chemical sensors.

    Shiwei Lin is a professor in the School of Materials Science and Engineering at Hainan University, China. He received his PhD in the University of Manchester in 2006. He received his B.S. and MSc degrees in Materials Science and Engineering from Tsinghua University (1996–2002). He joined Hainan University since 2007. His research interests focus on rational design and structure modification of photoelectrochemical materials and devices, chemical sensors and computational materials science.

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