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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.

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 poly(2,5-dimethoxyaniline)-based DLH prove the existence of energy barriers at the interfaces, as demonstrated by impedance spectroscopy. It exhibits a particularly interesting sensitivity to ammonia, at room temperature and in a broad relative humidity range. Thanks to its higher energy barriers, the poly(2,5-dimethoxyaniline)/LuPc2 DLH is the most sensitive device with a limit of detection of 320 ppb. This work paves the way for the use of substituted polyanilines in conductometric sensors not only in the field of air quality monitoring but also in the field of health diagnosis by measurement in human breath.

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 of the unsubstituted PANI. At pH 1.85 was different; no anion upload was observed during the electron transfer, but 1 H+ per electron was involved during the transition between the leucoemeraldine and emeraldine base forms. It should also be noted that the oxidation of the emeraldine into the pernigraniline form was not accessible in PTFANI because of the electron-withdrawing effects of the fluorine atoms. However, we took advantage of the unique behavior of PTFANI to build heterojunctions, by combining with a highly conductive molecular material, namely lutetium bisphthalocyanine, LuPc2. The obtained double-lateral heterojunction exhibited a particularly interesting sensitivity to ammonia, even under humid atmospheres, with a limit of detection of 450 ppb. This work paves the way for the use of PTFANI in other electronic devices and as a sensor not only in the field of air quality monitoring but also in the field of health diagnosis in measuring the human breath.

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 between the sublayer and the electrodes also plays a key role. They, furthermore, provide complementary data for the selective detection of ammonia and relative humidity in air.

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 played by the n-type TPDO sublayer. The device exhibits a response stable over time and can operate in a broad range of relative humidity.

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 prepared with small counterions, with a stable response in a broad range of relative humidity.

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-functionalized sample displays the largest response owing to both its hydrophilic nature, favoring the interaction with H2O molecules, and its largest surface area. Compared to data available in the literature, the present sensors display a remarkable sensitivity well below the ppm range, which makes them quite promising for environmental and medical applications, where NH3 concentrations (mostly of the order of tens of ppb) have to be detected.

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 Insulator heterojunctions (MSDIs) in association with the highly conductive lutetium bisphthalocyanine, LuPc2. Whereas the octaester derivative and Zn(T4F12Pc) exhibited a negative response to ammonia, as expected for p-type materials, Cu(F8Pc) exhibited a particular behavior. At low humidity levels, 30 and 10% rh, the current of the Cu(F8Pc)/LuPc2 MSDI decreases, similarly to p-type devices, but at higher relative humidity values, 70% rh, the current increases under ammonia, which is the signature of a n-type behavior. This ambipolar behavior is unique amongst semiconducting sensing materials. This work opens the way to the study of ambipolar materials as sensing materials for the development of a new type of conductometric gas sensors.

Interest in molecular materials has been driven in large part by their various and prosperous applications, especially in the domain of organic electronics, where they offer many advantages as well as alternative approaches compared to their inorganic counterparts. Most of conductometric transducers are resistors[[ and transistors[[[, but rarely diodes[6]. In our laboratory, we designed and characterized new molecular material based devices. Molecular Semiconductor Doped Insulator (MSDI) heterojunctions were built around a heterojunction between a Molecular Semiconductor (MS) and a Doped Insulator (DI)[7][8]. This new device exhibits interesting electronic properties that allow ammonia sensing in a large humidity range at room temperature.

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 transport properties too. The effect of the grafting of four different aromatic moieties bearing electron-donating and electron-withdrawing substituents is studied. One important feature is that the sensing properties are highly improved compared to the unmodified devices. Thus, the electrografting of dimethoxybenzene doubles the relative response of the heterojunction towards 90 ppm NH3, as well as the sensitivity in the range 1–9 ppm. This electrografting allows attaining a limit of detection as good as 140 ppb. The modified heterojunctions favorably compete other conductometric transducers for the detection of ammonia, at room temperature and in a broad range of relative humidity.

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 been historically the most commonly exploited way for the detection and quantification of gas pollutants. Herein, we focus on new transducers, either based on the well-known OFETs, or on transducers combining two molecular materials, namely the p–n junctions and the brand new molecular semiconductor–doped insulator (MSDI) heterojunctions. The sensitivity of the devices is demonstrated through the detection of ammonia and ozone in the range of ppm and ppb, respectively.

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 new chemical sensors, associated with electrochemical, conductometric or optical transducers.

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 particularly promising materials for the development of new chemical sensors, associated with both conductimetric and optical transducers.

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

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 10-70% RH range. Finally, CoPc offers a promising perspective as sensing material for air quality control applications, even at relatively high humidity levels.

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 in various fields of research.

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.

A smectogenic 1,3-bis(4-decyloxyphenyl)-3H-imidazol-1-ium trifluoromethane sulfonates (1) was studied on the drift mobility of carriers by a Time-Of-Flight (TOF) technique. The transient photocurrent decay curves were clearly observed for the positive electrode illumination and the transit times could be detected to indicate the mobility in the smectic A (SmA) phase is on the order of 10−3 cm2 V−1 s−1. This carrier mobility is too fast if it is a reflection of ionic transport in this system and is more easily explained on the basis of electronic charge hopping process.

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 a decrease in the case of LuPc2 resistors, as previously observed for other MSDIs with a n-type sublayer. At first, we showed the significant effect of the applied potential on the response of these sensors. There is an optimum operating point for which the response to ammonia is maximized, which depends on the nature of the samples. The influence of the thickness of the layers was studied, showing a strong influence of this parameter on the sensing properties. MSDIs prepared with fluorinated PTCDI exhibit a higher energy barrier and a lower current. Finally, in general, PTCDA/LuPc2 MSDIs show a strong response to ammonia with a response up to 250% to 30 ppm NH3 at 50% of relative humidity for the MSDI PTCDA/LuPc2 50 nm/50 nm. A discrimination better than 10 ppm between the ammonia concentrations was observed, regardless of relative humidity between 10 and 70% rh.

1,3-Bis(4-alkyloxyphenyl)-3H-imidazol-1-ium trifluoromethanesulfonates, alkyl = CH3(CH2)n–1, n = 8, 10, 12, 14 and 16, can be derived from the analogous 4-alkyloxyphenylamines. These imidazolium salts exhibit a lamellar liquid-crystal mesophase between 99 °C and 191 °C. The smectic-A phase was fully characterised by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. We report also the synthesis, lamellar crystal structure and catalytic activity of the PdII complex of the (deprotonated) carbene form of one of these salts. In addition, we measured the charged carrier mobilities in the mesophase.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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, leading to a variable extent of the plateau in the current-voltage characteristics, according to materials. We use this new transducer to detect different gases. We studied, in particular, the response of MSDIs to ammonia in a broad range of relative humidity (rh). A n-MSDI exhibits a positive response to ammonia (electron donating species) and a negative response to ozone (oxidizing species). Whereas the only material in contact with the gas is a p-type MS (LuPc2), these responses are opposite to those of a resistor prepared by only this material (LuPc2). The better stability toward humidity was obtained with Cu(F16Pc) as n-type sublayer. Thus, for Cu(F16Pc)/LuPc2 MSDI (50 nm/50 nm), the relative response to NH3 is almost not affected by the variation of rh in the 20-80 % range.

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.

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 film, but was too insulating to be interesting. We also prepared PANI-CuTsPc hybrid films by LBL technique. It allowed a regular deposition as evidenced by the linear increase of the absorbance at 688 nm as a function of the number of bilayers. The sensitivity to ammonia (NH3) of PANi-CuTsPc resistors was very high compared to that of individual materials, giving up to 80% of current decrease when exposed to 30 ppm NH3. Contrarily to what happens with neutral polymers, in PANI, CuTsPc was stabilized by strong electrostatic interactions, leading to a stable response to NH3, whatever the relative humidity in the range 10%-70%. Thus, the synergy of PANI with ionic macrocycles used as counteranions combined with their simple aqueous solution processing opens the way to the development of new gas sensors capable of operating in real world conditions.

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 particularly promising materials for the development of new chemical sensors, associated with both conductimetric and optical transducers.

The preparation of 1,3-bis-(4-dodecyloxy-phenyl)-3H-imidazol-1-ium trifluoro-methanesulfonate is described from the 4-dodecyloxy phenylamine derivative. This new imidazolium salt exhibits a lamellar liquid crystal mesophase between 119 and 172 °C. The Smectic A phase has been characterised by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. In addition the lamellar crystallographic structure obtained on single crystal is reported and corroborated the self-assembly of molecules in the mesomorphic state.

Wenowpresentastrategyforamoreversatileexploita-tionofliquid-crystaltemplateeffects,whichisillustratedbythe electrolysis of imidazolium liquid crystals containingdicyanoargentate(I)anddicyanoaurate(I)anionstoproducesilverandgoldnanoparticles.Thekeytothisapproachisthecouplingoftheself-organizationoftheimidazoliummetallatetotheuseofelectrochemicalreduction,thelatterprovidingthe means to control the particle size and form of theelectrodeposited metals by variation of parameters such asthepotentialandthecurrentdensity.Many mesomorphic imidazolium salts can be readilypreparedbysimplemetathesisreactionsinvolvingprecipita-tion from aqueous solutions containing the appropriateanions. In investigating this chemistry, we sought to useanionsincorporatingtransitionmetalstoendowtheproductswith properties such as redox activity and variable conduc-tivity.Thus,wehavesynthesizeddicyanoargentate(I)(1)anddicyanoaurate(I)(2)derivativesof3-(4-dodecyloxybenzyl)-1-methyl-1H-imidazolium in good yield(over 80%) from thebromidestartingmaterial(Scheme1).

The molecular semiconductors have enabled the production of electronic devices such as field effect transistors, diodes and other heterojunctions. The ambipolar materials, capable of carrying both positive charges and negative, result in devices with special properties. The purpose of this thesis is to synthesize new ambipolar materials develop original electronic devices, especially for applications in the field of gas sensors. We are interested in molecules capable to lead to thin films with low temperature techniques known as solution processing, particularly metallo-phthalocyanines., Les semi-conducteurs moléculaires ont permis la réalisation de dispositifs électroniques, tels que transistors à effet de champ, diodes et autres hétérojonctions. Les matériaux ambipolaires, capables de transporter tant les charges positives que négatives, conduisent à des dispositifs aux propriétés particulières. L’objet de cette thèse est de synthétiser de nouveaux matériaux moléculaires ambipolaires et de développer des dispositifs électroniques originaux, en particulier pour des applications dans le domaine des capteurs de gaz. Nous nous intéressons aux molécules compatibles avec des mises en forme par des techniques dites de solution processing, en particulier des métallo-phtalocyanines.