Factors that influence the performance of hydrogen detectors based on single-wall carbon nanotubes
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摘要: 单壁碳纳米管用于制造氢气传感器已有几十年的历史。由于单壁碳纳米管与氢气的相互作用很小，因此需采用了多种改性来辅助，改性物包括金属、金属氧化物与聚合物等。一些研究指出，当与碳纳米管上的官能团结合时，改性物可以使响应提高几个数量级。在目前的研究中，已开发了许多新的结构。此外，单壁碳纳米管的直径和手性等结构也会影响氢气探测器的性能。本文对单壁碳纳米管的改性进行了分类，并对其影响因素进行了讨论，旨在为制造高响应度和低检测限的探测器提供支撑。Abstract: Single-wall carbon nanotubes (SWCNTs) have been used to fabricate hydrogen gas (H2) detectors for several decades. It has been proven that they barely interact with H2 so that numerous modifications are used to assist this function. Additives include metals, metal oxides, polymers etc. Previous research suggests that the presence of functional groups on the SWCNTs may improve the response by several orders of magnitude. Recently, many different novel structures have been exploited, and structural parameters of the SWCNTs, such as diameter and chirality, also influence the performance of the detectors. Modifications of the SWCNTs are classified and other factors that influence the performance are also discussed, with the aim of accelerating the manufacture of detectors with a high responsivity and low limit of detection.
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Key words:
- Gas sensors /
- Single-walled carbon nanotubes /
- Modification /
- Self-characteristic /
- Air monitoring
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Figure 1. (a) Response curve of an individual SWCNTs coated with Pd particles to 4.0×10−4 H2 on and off cycles in air (left) and to 0.4×10−4 H2 self-recovery in air (right). Reproduced with permission from Ref[20], Copyright from WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2001. (b) I-V characteristics showing the resistance change with increase in amount of charge used for Pd of electrodeposition. Reproduced with permission from Ref[21], Copyright from 2007 American Chemical Society
Figure 2. (a) Response curves of for 6% H2 at different temperatures. Reproduced with permission from Ref[16], Copyright from 2010 Elsevier B.V. (b) Response curves of 0.15×10−2 H2 for SnO2 and SWCNTs/SnO2 at different temperatures, respectively. Reproduced with permission from Ref[22], Copyright from 2007 Elsevier B. Response curves of (c) SnO2-SWCNTs and (d) Pt-SnO2-SWCNTs films with different transparencies in 1%-6% H2. Reproduced with permission from Ref[19], Copyright from 2012 Elsevier B.V. Response curves of (e) the Pd-SWCNTs film/SiO2/p-Si heterostructure for 0.02% H2 and (f) the Pd-SWCNTs film resistance-type device for 0.05% H2. Reproduced with permission from Ref[34], Copyright from 2015 Author (s)
Figure 3. (a) A schematic illustration of a film of SWCNTs-based on a glass substrate. (b) Interactions of H2 with the Type III sensor. Reproduced with permission from Ref[36], Copyright from 2010 Elsevier B.V. (c) Response of Pd-SWCNTs and Pd-exfoliated SWCNTs thin films during repeated H2 on and off with an H2 concentration of 4% in air. Reproduced with permission from Ref[46], Copyright from 2007 Elsevier B.V. (d) The image of Pd random decoration of the s-SWCNTs at different position, response of the defective device. Reproduced with permission from Ref[47]. Copyright from 2010 American Chemical Society
Figure 4. (a) The response of CNT-Pd nanoparticles H2 sensor with the deposition of four QPd values: showing three different of H2 concentration: Left, 0.1×10−4 < [H2] < 0.1×10−3; Middle, 0.1×10−3 < [H2] < 0.1×10−2, Right, 0.2×10−2 < [H2] < 0.4×10−1. (b) The image of a single CNT rope decorated with Pd nanoparticles. Reproduced with permission from Ref[48], Copyright from American Chemical Society
Figure 5. (a) Conductivity to different H2 concentrations. Reproduced with permission from Ref[49], Copyright from 2003 Nature Publishing Group. (b) Response curves of at different diameter and chirality SWCNTs/Pd FETs on Si/SiO2. Reproduced with permission from Ref[37], Copyright from 2011 American Chemical Society. (c) Changes of the valence band of Schottky barrier with various H2 concentrations. Reproduced with permission from Ref[49], Copyright from 2003 Nature Publishing Group. (d) The diameter of SWCNTs increases from large to small, but the performance increases from low to high to low. (e) The relationship between the diameter and conductivity of different chiral carbon nanotubes in three s-SWCNTs FETs. Reproduced with permission from Ref[37], Copyright from 2011 American Chemical Society. (f) The image of the Pd-decorated SWCNTs film H2 sensor. (g) Real time response to different H2 concentrations at room temperature. (h) Response time and decay time can be defined by fitting portions of the curves. Reproduced with permission from Ref[13], Copyright from American Chemical Society
Table 1. Characteristics of various SWCNT-Based H2 Sensors
Sample LOD Temperature Concentration range Response time Refs SWCNTs-Pd-functionalized 0.5% RT 0.5% - 3% ~ 2 min [31] SWCNTs-Pd 1% RT / 20 s [25] SWCNTs-Pd-functionalized 0.3% RT 0.5% - 4% ~10 min [32] SWCNTs-Pd- Electrochemical 1.0×10−5 RT 0.1×10−4 - 0.15×10−3 3 min [29] SWCNTs-Pd 1% RT 0.05% - 1% 3 s [30] SWCNTs-Pd 1% RT 0.3×10−4 - 1×10−3 1.5 s [12] SWCNTs/Pd-grafted 1% RT 0.001% - 1% 7 s [27] SWCNTs-COOH-Pd 1.0×10−4 RT 0.3×10−4 - 0.3×10−3 20 min [21] SWCNTs-Pd 2.5% RT 0.025% - 2.5% 5 s [28] SWCNTs-Pd 0.7×10−7 / / / [24] SWCNTs/DNA/Pd 1.0×10−4 RT 1×10−4 - 1×10−3 13 min [36] s-SWCNTs-Pd 8.9×10−7 RT 0.89×10−7 - 0.311×10−3 7 s [13] SWCNTs/Pd 0.73×10−6 RT 0.73×10−6 - 0.5×10−4 3.6 min [37] SWCNTs/Pd 0.74×10−7 RT 0.25×10−4 - 0.2×10−3 11.8 min [38] SWCNTs/SnO2 1.5×10−3 250 °C 0.3×10−3 - 0.5×10−3 2-3 s [39] SWCNTs/CuO 6% 250 °C >6% ~1.2 min [16] SWCNTs/SnO2 1% RT >1% 2-3 s [18] SWCNTs/SnO2-Pt 6% 200 °C 1% - 6% <40 s [19] SWCNTs/SiO2/Si-Pd 0.05% RT 0.02% - 0.1% ~552 s [35] 
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