0000000000000794
AUTHOR
Jean-moïse Suisse
From the solution processing of hydrophilic molecules to polymer-phthalocyanine hybrid materials for ammonia sensing in high humidity atmospheres.
We have prepared different hybrid polymer-phthalocyanine materials by solution processing, starting from two sulfonated phthalocyanines, s-CoPc and CuTsPc, and polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), poly(acrylic acid-co-acrylamide) (PAA-AM), poly(diallyldimethylammonium chloride) (PDDA) and polyaniline (PANI) as polymers. We also studied the response to ammonia (NH3) of resistors prepared from these sensing materials. The solvent casted films, prepared from s-CoPc and PVP, PEG and PAA-AM, were highly insulating and very sensitive to the relative humidity (RH) variation. The incorporation of s-CoPc in PDDA by means of layer-by-layer (LBL) technique allowed to stabilize the fi…
Electrochemical deposition of aniline derivatives for conductometric gas sensors
International audience; Polymer film of poly(2,3,5,6-tetrafluoroaniline) (PTFA) were electroplated on ITO substrate from acidic medium by chronoamperometry. Electrochemical and morphological characterizations were performed and compared to polyaniline properties similarly coated. It seemed that PTFA film had an irreversible redox response with poor conductivity due to the absence of acid-base doping. This film were then incorporated in a patented device called MSDI heterojunction to perform ammonia sensing in humid atmosphere.
Modulation of the organic heterojunction behavior, from electrografting to enhanced sensing properties
International audience; The energy barrier of an organic heterojunction built on ITO electrodes and made from a low conductive sublayer (Cu(F16Pc)) covered by a highly conductive semiconductor (LuPc2) is modulated by electrografting of organic layers before depositing the sublayer. Impedance spectroscopy clearly demonstrates the increase of the energy barrier at the ITO – sublayer interface. Additionally, the electrografting is a versatile and promising method for the tuning of heterojunctions. The I(V) characteristics of the heterojunctions are highly modified by the electrografting. The same electromodifications of electrodes carried out on LuPc2 resistors lead to a modification of their …
Deposition and production of highly reproducible hybrid Cu[(tBu)4Pc]-polystyrene thin layers via spin casting
This study focuses on the determination of a protocol for the production of a hybrid material composed of a polymer and a macrocyclic complex, namely polystyrene and a tetra-tert-butyl-copper phthalocyanine (Cu[(tBu)4Pc]), in order to obtain a layer thickness of about 100 nm and a controlled porosity in a highly reproducible way. Several methods were implemented and their reproducibility was evaluated through elements of characterization such as optical microscopy, atomic force microscopy and scanning electron microscopy. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers
Conducting Polymers for Ammonia Sensing: Electrodeposition, Hybrid Materials and Heterojunctions
International audience; Polyaniline (PANI) with electrodonating and electrowithdrawing substituents were electrodeposited and studied as sensing materials in resistors and heterojunctions. Whereas the dimethoxyaniline leads to a highly conductive material, the tetrafluoroaniline leads to a poor conducting polymer. However, this latter was used in heterojunctions, associated with a highly conductive material, the lutetium bisphthalocyanine LuPc2. Elsewhere, hybrid materials combining polypyrrole (PPy) with ionic macrocycles as counterions were also electrosynthesized and used as sensing material in resistors, for the detection of ammonia. They exhibit a higher sensitivity compared to PPy pre…
Selective quantification of humidity and ammonia by optical excitation of molecular semiconductor-doped insulator (MSDI) sensors
MSDI (molecular semiconductor-doped insulator) ammonia sensors have been investigated using cyclic optical excitation as multi-signal generation method. This method enables a selective quantification of both humidity in the range of 30–70 %rh and ammonia concentration in the range of 0–30 ppm with a single sensor at room temperature.
Lanthanide macrocyclic complexes: from molecules to materials and from materials to devices
In the present review, we show how the chemistry of lanthanide macrocyclic complexes, which began almost 50 years ago in Russia, is still very active. Additionally to bisphthalocyanines complexes, triple-decker, but also quadruple- and quintuple-decker complexes have been synthesized via new chemical routes. The driving force for the development of this chemistry arises from the wide range of possible applications. Owing to their very high conductivity, compared to that of monophthalocyanines, LnPc2 and Ln2Pc3 complexes are used as molecular semiconductors in electronic devices. The radical nature of LnPc2 complexes makes them easily oxidized and reduced. This is the reason why they are pa…
The multimodal detection as a tool for molecular material-based gas sensing
Abstract The adsorption of a target gas on a material induces a change in several physical characteristics, such as the dielectric constant, the work function or the conductivity. The use of different transducers sensitive to the variation of these parameters appears to be a relevant methodology worthy of investigation. In the field of sensors, molecular materials present interesting and potentially valuable features as sensing elements for real gas sensor applications. In this article, we review the different types of conductimetric transducers and also show how a molecular material-based microwave transducer can be used for gas sensing. Among conductimetric transducers, resistors have bee…
Low Conductive Electrodeposited Poly(2,5-dimethoxyaniline) as a Key Material in a Double Lateral Heterojunction, for Sub-ppm Ammonia Sensing in Humid Atmosphere
We present a new device called a double lateral heterojunction (DLH) as an ammonia sensor in humid atmosphere. It combines polyaniline derivatives in their poor conducting state with a highly conductive molecular material, lutetium bisphthalocyanine, LuPc2. Polyaniline and poly(2,5-dimethoxyaniline) are electrodeposited on ITO interdigitated electrodes, leading to an original device that can be obtained only by electrochemistry and not by other solution processing techniques. Both polymers lead to highly conducting materials that require a neutralization step before their coverage by LuPc2. While the device based on polyaniline shows ohmic behavior, the nonlinear I- V characteristics of the…
New n-type molecular semiconductor–doped insulator (MSDI) heterojunctions combining a triphenodioxazine (TPDO) and the lutetium bisphthalocyanine (LuPc2) for ammonia sensing
International audience; Molecular semiconductor–doped insulator (MSDI) heterojunctions were designed using a new family of sublayers, namely triphenodioxazines (TPDO). The device obtained by combining the tetracyano triphenodioxazine bearing two triisopropylsilylethynyl moieties as a sublayer with the lutetium bisphthalocyanine (LuPc2) as a top layer showed a nonlinear current–voltage characteristic independent of the sign of the polarization, which is the signature of MSDI heterojunctions. Thus, a TPDO was used in a chemical sensor for the first time. Despite LuPc2 being the only material exposed to the atmosphere, the positive response of the device under ammonia revealed the key role pla…
Imidazolium-based liquid crystals: a modular platform for versatile new materials with finely tuneable properties and behaviour
Ionic liquid Crystals constitute highly versatile materials that have drawn much interest these past few years in the fields of academic research and industrial development. In this respect, the present article is intended as an update of K. Binnemans review published in 2005, but focusing exclusively on the imidazolium cation - the most widely studied. Herein, imidazolium-containing thermotropic liquid crystalline materials will be sorted by molecular structure (mono-, bis-, poly-imidazolium compounds, with symmetrical and non-symmetrical structures) and discussed. Their physico-chemical properties will be exposed in order to adduce the relevancy and potential of the imidazolium platform i…
Bias and humidity effects on the ammonia sensing of perylene derivative/lutetium bisphthalocyanine MSDI heterojunctions
International audience; In this paper, we prepared and studied sensors based on Molecular Semiconductor-Doped Insulator (MSDI) heterojunctions. These original devices are built with two stacked layers of molecular materials and exhibit very specific electrical and sensing properties. We studied the properties of a MSDI composed of the perylenetetracarboxylic dianhydride, PTCDA, or the fluorinated perylenebisimine derivative, C4F7-PTCDI, as n-type molecular material sublayers, and LuPc2 as a p-type semiconductor top layer. Their response to ammonia was compared to that of a resistor formed of only the top layer of the MSDI (LuPc2). Ammonia increases the current in the MSDIs whereas it causes…
Comprehensive Study of Poly(2,3,5,6-tetrafluoroaniline): From Electrosynthesis to Heterojunctions and Ammonia Sensing.
In this work, we report for the first time on a comprehensive study of poly(2,3,5,6-tetrafluoroaniline) (PTFANI). Contrary to the nonfluorinated polyaniline (PANI) or its analogues bearing one fluorine atom, PTFANI is a poorly conductive material. We present a comprehensive study of the electrosynthesized PTFANI from its monomer in an acidic aqueous medium. PTFANI was fully characterized by a potential-pH diagram, spectroelectrochemistry, and electrochemical quartz crystal microbalance (EQCM) measurements, as well as by a morphological study. Combined with the X-ray photoelectron spectroscopy (XPS) analysis, it allowed us to understand the redox properties of this polymer compared to those …
Revisiting the electronic properties of Molecular Semiconductor – Doped Insulator (MSDI) heterojunctions through impedance and chemosensing studies
Abstract The core activity of this work was to give a new interpretation of the electronic behavior of Molecular Semiconductor – Doped Insulator heterojunctions (MSDI), a new organic device combining two molecular materials with very different electronic properties. We focused on understanding the phenomenon occurring at the interface of fluorinated and non-fluorinated phthalocyanines that appears to be a determining factor for the electronic charge transport in the two-component thin film and ultimately deciding the nature of gas sensing, as illustrated with ozone and ammonia chosen as examples of accepting and donating gases. The impedance measurements showed that the Schottky contact bet…
Differential study of substituted and unsubstituted cobalt phthalocyanines for gas sensor applications
Abstract The conductivity of CoPc (cobalt phthalocyanine) and Co[(SO3Na)2,3Pc] was measured under a flow of two different gases (NH3 and O3), during exposure/recovery cycles. It appears that the relative responses are linearly related to the concentration, in the 20–200 ppb range for O3 and in the 20–200 ppm range for NH3. Observed during time, the sensing parameters allow a qualitative understanding of the kinetics. The comparative study of those products under both different gases gave interesting results for sensor applications. Whereas CoPc is sensitive to both gases, its sulfonated counterpart is only sensitive to NH3.
Phthalocyanine-based hybrid materials for chemosensing
In the present review, we show how the chemical variability of phthalocyanines allowed to synthesize a broad range of hybrid materials. The combination of phthalocyanines or related derivatives with polymers or carbonaceous materials led to efficient chemical sensors. It is shown how the incorporation of macrocyclic molecules in hybrid materials highly modifies the structural and morphological characteristics of the materials. Rugosity, specific surface and porosity being key parameters in the analyte-sensing material interactions, these modifications highly improve the performance of chemical sensors. This is the reason why they are particularly promising materials for the development of …
Humidity-enhanced sub-ppm sensitivity to ammonia of covalently functionalized single-wall carbon nanotube bundle layers
International audience; A low-cost method for carbon nanotubes (CNTs) network production from solutions on flexible polyethylene naphthalate substrates has been adopted to prepare high quality and well characterized SWCNT bundle layers to be used as the active layer in chemiresistor gas sensors. Two types of SWCNTs have been tested: pristine SWCNTs, deposited from a surfactant solution, and covalently functionalized SWCNTs, deposited from a dimethyl-acetamide solution. The humidity effects on the sensitivity of the SWCNTs network to NH3 have been investigated. The results show that relative humidity favors the response to NH3, confirming recent theoretical predictions. The COOH-functionaliz…
On the interest of ambipolar materials for gas sensing
International audience; Based on the electrochemical properties of a series of metallophthalocyanines this article shows that the phthalocyanine bearing four alkoxy groups and twelve fluorine atoms behaves approximately as those with eight fluorine atoms. This indicates that the electron-donating effect of one alkoxy group balances the electro-withdrawing effect of one fluorine atom. We engaged three metallophthalocyanines, namely the octafluoro copper phthalocyanine, Cu(F8Pc), an octaester metallophthalocyanine and a phthalocyanine bearing four alkoxy groups and twelve fluorine atoms, Zn(T4F12Pc), in building original conductometric transducers that are Molecular Semiconductor – Doped Insu…
ChemInform Abstract: Lanthanide Macrocyclic Complexes: From Molecules to Materials and from Materials to Devices.
In the present review, we show how the chemistry of lanthanide macrocyclic complexes, which began almost 50 years ago in Russia, is still very active. Additionally to bisphthalocyanines complexes, triple-decker, but also quadruple- and quintuple-decker complexes have been synthesized via new chemical routes. The driving force for the development of this chemistry arises from the wide range of possible applications. Owing to their very high conductivity, compared to that of monophthalocyanines, LnPc2 and Ln2Pc3 complexes are used as molecular semiconductors in electronic devices. The radical nature of LnPc2 complexes makes them easily oxidized and reduced. This is the reason why they are par…
Humidity effect on ammonia sensing properties of substituted and unsubstituted cobalt phthalocyanines
In this paper, we studied the effect of humidity on the response of cobalt phthalocyanine-containing resistors to ammonia, in the ppm range. We pointed out the fact that, when alternating exposure periods with recovery periods, the humidity effect had to be carefully studied, in correlation with the flow variation. Thus, for a sulfonated cobalt phthalocyanine, the effect of NH(3) was totally screened as soon as the relative humidity (RH) was above 10%. On the contrary, when using unsubstituted cobalt phthalocyanine (CoPc) as sensing material, the sensors' response to NH(3) appears to be quite stable in a wide RH range, allowing a discrimination between 12, 25 and 50 ppm of NH(3) over the 10…
Molecular Semiconductors — Doped Insulator (MSDI) heterojunctions as new conductometric devices for chemosensing in wet atmosphere.
Most of the gas sensors are based on resistors with inorganic materials and more rarely on other conductometric devices (diodes or transistors). Conductometric sensors have also been designed with molecular materials. Thus, in 2009, Molecular Semiconductor — Doped-insulator (MSDI) heterojunctions were built around a heterojunction between a molecular semiconductor (MS) and a doped-insulator (DI). The MS must be more conductive than the sublayer to take advantage of the heterojunction. The MS is generally of p-type and DI can be of p-type (p-MSDI) or n-type (n-MSDI) material. The energy barrier at the interface depends on the difference in the charge carrier density in the two layers, leadin…
CCDC 1497477: Experimental Crystal Structure Determination
Related Article: Amélie Wannebroucq, Rita Meunier-Prest, Jean-Claude Chambron, Claire-Hélène Brachais, Jean-Moïse Suisse, Marcel Bouvet|2017|RSC Advances|7|41272|doi:10.1039/C7RA05325H