Covalent grafting of aryls to modulate the electrical properties of phthalocyanine-based heterostructures: Application to ammonia sensing

Kumar, Abhishek; Meunier‐Prest, Rita; Herbst, Frédéric; Heintz, O.; Lesniewska, Éric; Bouvet, Marcel

doi:10.1016/j.cej.2022.135207

Cited by 24 publications

(17 citation statements)

References 62 publications

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“…[18] As a consequence, sensor performance toward NH 3 gas demonstrated an improvement in sensitivity, reproducibility, response/recovery kinetics, and operational stability compared to existing chemiresistors. [19,20] A wide range of molecular semiconductors and polymers have been investigated as active sensing materials in organic heterojunction sensors for NH 3 detection including metal phthalocyanines (MPc), polyporphyrins, [21,22] perylene derivatives, [23] and triphenodioxazine. [24] MPcs are thermally stable conjugated macrocycles with favorable semiconducting properties making them ideal for use in organic heterojunction sensors, besides other areas of organic electronics such as organic thin-film transistors (OTFTs) and organic photovoltaics (OPVs).…”

Section: Introductionmentioning

confidence: 99%

Molecular Engineering of Silicon Phthalocyanine to Improve the Charge Transport and Ammonia Sensing Properties of Organic Heterojunction Gas Sensors

Moorthy

King

Kumar

et al. 2022

Advanced Sensor Research

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Novel organic heterostructures fabricated with a bilayer consisting of an axially substituted silicon phthalocyanine (R 2 -SiPc) derivative and lutetium bis-phthalocyanine (LuPc 2 ) are investigated for their ammonia sensing properties. Surface and microstructure characterization of the heterostructure films reveal either compact or highly porous surface topography in (345F) 2 -SiPc and Cl 2 -SiPc-based heterostructures, while electrical characterization reveals a strong influence of the axial substituent in R 2 -SiPc on NH 3 sensing capabilities. Electrical characterization further demonstrates an apparent energy barrier for interfacial charge transport, which is higher in the (345F) 2 -SiPc/LuPc 2 heterojunction device. In-depth charge transport studies by impedance spectroscopy further reveal a resistive interface in (345F) 2 -SiPc/LuPc 2 and faster bulk and interfacial charge transport in Cl 2 -SiPc/LuPc 2 heterojunction devices. Different interfacial charge transport capabilities and surface topographies affect NH 3 sensing properties of the two heterojunction devices, in which (345F) 2 -SiPc/LuPc 2 reveals a fast and non-linear response with a limit of detection (LOD) of 310 ppb, while Cl 2 -SiPc/LuPc 2 exhibits a slow, and linear response to NH 3 with LOD of 100 ppb. Finally, different metrological parameters of the two sensors are correlated to the respective gas-material interactions, in which adsorption and diffusion regimes are modulated by the surface topography and hydrophobicity of the sensing layer.

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Section: Introductionmentioning

confidence: 99%

Molecular Engineering of Silicon Phthalocyanine to Improve the Charge Transport and Ammonia Sensing Properties of Organic Heterojunction Gas Sensors

Moorthy

King

Kumar

et al. 2022

Advanced Sensor Research

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“…Deniau et al 42 reported a direct reaction of diazonium salts with the gold surface with the formation of aryl cations grafting on the substrate, as observed by XPS analyses. Bouvet et al 43 performed diazonium grafting to form nine aryls bearing different substituents on indium tin oxide (ITO). XPS confirmed the aryl/polyaryl films and a covalent linkage on the ITO surface.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Visualizing Water Reduction with Diazonium Grafting on a Glassy Carbon Electrode Surface in a Water-in-Salt Electrolyte

Zhu

Droguet

Deng

et al. 2023

ACS Appl. Mater. Interfaces

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Aqueous batteries are regaining interest, thanks to the extended working stability voltage window in a highly concentrated electrolyte, namely the water-in-salt electrolyte. A solid-electrolyte interphase (SEI) forms on the negative electrode to prevent water access to the electrode surface. However, we further reported that the formed SEI layer was not uniform on the surface of the glassy carbon electrode. The SEI after passivation will also show degradation during the remaining time of opencircuit voltage (OCV); hence, it calls for a more stable passivation layer to cover the electrode surface. Here, a surface modification was successfully achieved via artificial diazonium grafting using monomers, such as poly(ethylene glycol), α-methoxy, ω-allyloxy (PEG), and allyl glycidyl cyclocarbonate (AGC), on glassy carbon. Physical and electrochemical measurements indicated that the hydrophobic layer composed of PEG or AGC species was well grafted on the electrode surface. The grafted hydrophobic coatings could protect the electrode surface from the water molecules in the bulk electrolyte and then suppress the free water decomposition (from LSV) but still migrating lithium ions. Furthermore, multiple cycles of CV with one-hour resting OCV identified the good stability of the hydrophobic grafting layer, which is a highlight compared with our precious work. These findings relying on the diazonium grafting design may offer a new strategy to construct a stable artificial SEI layer that can well protect the electrode surface from the free water molecule.

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“…4a) are much higher, compared to the small electrode-based device. Thus, a broader conclusion can be Nyquist plots were modelled by constant phase element (CPE)-based equivalent circuit, considering the distributed microstructural properties of the heterostructure [46,47]. Different charge transport parameters such as resistance, alpha (α) and effective capacitance (Ceff) were determined from the modelling to predict the electrical nature of the heterojunction devices.…”

Section: Electrical Properties Of Heterojunctionmentioning

confidence: 99%

“…Notably, the calibration curves are not linear for both the sensors and the rate of increase in the RR experiences an exponential decay with increasing NH3 concentrations. Such behavior of the sensors is attributed to the limited number of available active sites on the sensors surface, which tend to saturate with increasing ammonia concentrations [47].…”

Section: Ammonia Sensing Propertiesmentioning

confidence: 99%

Interplay of electrode geometry and bias on charge transport in organic heterojunction gas sensors

Kumar

Meunier‐Prest

Lesniewska

et al. 2022

Sensors and Actuators B: Chemical

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Covalent grafting of aryls to modulate the electrical properties of phthalocyanine-based heterostructures: Application to ammonia sensing

Cited by 24 publications

References 62 publications

Molecular Engineering of Silicon Phthalocyanine to Improve the Charge Transport and Ammonia Sensing Properties of Organic Heterojunction Gas Sensors

Molecular Engineering of Silicon Phthalocyanine to Improve the Charge Transport and Ammonia Sensing Properties of Organic Heterojunction Gas Sensors

Visualizing Water Reduction with Diazonium Grafting on a Glassy Carbon Electrode Surface in a Water-in-Salt Electrolyte

Interplay of electrode geometry and bias on charge transport in organic heterojunction gas sensors

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