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…

Tuning of interfacial charge transport in polyporphine/phthalocyanine heterojunctions by molecular geometry control for an efficient gas sensor

Abstract Owing to high interfacial conductivity, organic heterostructures hold great promises to augment the electrical performances of electronic devices. In this endeavor, the present work reports fabrication of novel polyporphine/phthalocyanine heterostructures and investigates the modulation of charge transport induced by structural change of polyporphine and its implication on ammonia sensing properties. Polyporphines materials are electrosynthesized by oxidation of zinc(II) porphine monomer that corresponds to the fully unsubstituted porphyrin. At less-positive anodic potential, low conducting meso,meso-singly-linked type-1 polymer (pZnP-1) is formed in which a monomer unit stays orth…

Molecular Material‐Based Conductimetric Gas Sensors

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 …

Growth mode and self-organization of LuPc2on Si(001)-2×1vicinal surfaces: An optical investigation

We report an investigation of the initial growth and of the self-organization of lutetium biphthalocyanine LuPc2 on Si(001)-2 x 1 vicinal surfaces. Using surface-sensitive optical spectroscopies, namely, surface-difference-reflectance spectroscopy (SDRS) and reflectance-anisotropy spectroscopy (RAS), together with local-probe microscopies, we are able to propose a scenario for the growth mode up to about 20 nm. We demonstrate that the growth mode initially proceeds through the formation of a wetting layer, followed by the formation of clusters whose sizes increase while keeping a constant shape in which the molecules are inclined. Moreover, the LuPc2 molecules are self-organized along the s…

Selectivity improvement of semi-conducting gas sensors by selective filter for atmospheric pollutants detection

International audience; The monitoring of atmospheric pollution using chemical gas sensors is a challenge due to the lack of selectivity of most existing devices. However, their performances can be improved using filtering films achieving the separation or the removal of some gases. This study is focused on the detection of carbon monoxide and of oxidant pollutants (nitrogen dioxide and ozone) by sensors constituted of SnO2, or phthalocyanine compounds. Two types of filters were investigated. Filters based on MnO2 powder are successful to remove ozone while preserving nitrogen dioxide in a large temperature range from ambient to 400 -C, but they partially convert carbon monoxide. The second…

Effects of metal–ligand coordination on the self-assembly behaviour of a crown ether functionalised perylenetetracarboxylic diimide

A novel perylenetetracarboxylic diimide (PDI) derivative, N,N′-di(4′-benzo-15-crown-5-ether)-1,7-di(4-tert-butyl-phenoxy)perylene-3,4;9,10-tetracarboxylic diimide (CRPDI), has been synthesised and characterised. Dimerisation of CRPDI is induced by the presence of K+ in CHCl3 or spontaneously occurs in methanol, as revealed by absorption and emission spectroscopy. In particular, the formation of co-facial dimer in the presence of K+ proceeds in a three-stage process, as indicated by absorption spectroscopy. The belt- and rope-like nanostructures of CRPDI fabricated from methanol and CHCl3 solution in the presence of K+ are obtained by scanning electron microscopy. Furthermore, the conductivi…

Molecular semiconductor-doped insulator (MSDI) heterojunctions: Oligothiophene/bisphtalocyanine (LuPc2) and perylene/bisphthalocyanine as new structures for gas sensing

Abstract The combination of a sexithiophene and a perylene diimide derivatives, as p-type and n-type materials, respectively, used as sub-layers, to an intrinsic semiconductor, namely the lutetium bisphthalocyanine, allows to obtain a new transducer for gas sensing. These transducers were called molecular semiconductor-doped insulator (MSDI) heterojunctions, were recently designed and reported, but with only phthalocyanines as active materials. p-Type material leads to MSDIs that exhibit a positive response to ozone and a negative response to ammonia, whereas MSDIs prepared from n-type material exhibit a positive response to ammonia and negative response to ozone. The remarkable point is th…

Organic Heterojunction Devices Based on Phthalocyanines: A New Approach to Gas Chemosensing.

Organic heterostructures have emerged as highly promising transducers to realize high performance gas sensors. The key reason for such a huge interest in these devices is the associated organic heterojunction effect in which opposite free charges are accumulated at the interface making it highly conducting, which can be exploited in producing highly sensitive and faster response kinetics gas sensors. Metal phthalocyanines (MPc) have been extensively studied to fabricate organic heterostructures because of the large possibilities of structural engineering which are correlated with their bulk thin film properties. Accordingly, in this review, we have performed a comprehensive literature surve…

Electrochemical and Spectroelectrochemical Behavior of a Tetracyanotriphenodioxazine in Solution and Thin-Films

International audience; We report the electrochemical behavior of a tetracyano triphenodioxazine bearing two triisopropylsilylethynyl moieties (TiPS‐TPDO‐tetraCN) during its reduction studied either in solution or after vacuum evaporation deposition on indium tin oxide (ITO) support. While in dichloromethane, it typically proceeds in two successive monoelectronic reactions, in acetonitrile, the mechanism appears more complex. Fine analysis of the spectroelectrochemical results combined with simulation of the voltammograms with various amount of water suggest the involvement of water and of a restructured dianion in the electrochemical process. In the solid‐state, the formation of the diprot…

Photon assisted-inversion of majority charge carriers in molecular semiconductor-based organic heterojunctions

International audience; Ambipolar molecular materials hold great promises as a building block of next generation highly efficient, less complex and low cost electronics devices. In this endeavor, the present work reports the fabrication of organic heterojunction devices based on halogenated copper Phthalocyanines (CuPc) and lutetium bisphthalocyanine (LuPc2) bilayer, investigates their structural and electrical properties and probes the ambipolar behavior by ammonia sensing. Microstructural analysis of the heterostructure thin films revealed compact and semicrystalline organization, depending on the number of halogen substituents in CuPc. The heterojunction devices reveal a non-linear I(V) …

Tuning Of Organic Heterojunction Conductivity By The Substituents' Electronic Effects In Phthalocyanines For Ambipolar Gas Sensors

Abstract Exploiting organic heterojunction effects in electrical devices are an important strategy to improve the electrical conductivity, which can be utilized into improving the conductometric gas sensors performances. In this endeavor, the present article reports fabrication of organic heterostructures in a bilayer device configuration incorporating octa-substituted nickel phthalocyanines (NiPc) and radical lutetium bis-phthalocyanine (LuPc2) and investigates their sensing properties towards NH3 vapor. NiPc having hexyl sulfanyl, hexyl sulfonyl and p-carboxyphenoxy moieties are synthesized, which electronic effects are electron donating, accepting and moderate accepting, respectively, al…

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…

High Tolerance of Double-Decker Phthalocyanine Towards Molecular Oxygen

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.

Electrochemistry of methylene blue at an alkanethiol modified electrode

International audience; Gold surfaces were derivatized with decanethiol. The electrochemistry of methylene blue at these modified electrodes was investigated in function of the gold cleaning process and compared with the results obtained at a bare gold electrode. Cyclic voltammetry at low methylene blue concentrations (c(MB) <= 16 mu M) yielded surface behavior data. The properties of the film vary with the electrode pretreatment. Without electrochemical cleaning step, the standard potential at a gold electrode modified with 1-decanethiol is nearly the same as on a bare gold electrode. On the other hand, when the electrode is electrochemically cleaned before adsorption of the alkanethiols, …

Les matériaux pour capteurs chimiques

National audience; A chemical sensor is composed of one part supplying chemical reco gnition coupled to one transducingsystem. At the recognition origin, interaction with the target chemical species is oftwo types, either electronicexchange, or ionic exchange. Two large classes of materials that can supply recognition proceed: metals andsemiconductors giving rise to electronic exchange and ionic conducting materials giving rise to ionic exchan-ge. This paper is structured in tw o large parts, emphasizing on materi als inducing specific interactions:semiconductor materials (metallic oxides and molecular semiconductors) and ionic conductor materials.In each part will be presented nature of ma…

Mass Transport in Nanoporous Gold and Correlation with Surface Pores for EC 1 Mechanism: Case of Ascorbic Acid

International audience; Entry for the Table of Contents Playing with the pores: Surface pores size in nanoporous gold modulates the electrode reactions pathways of ascorbic acid. The reaction is largely driven by diffusion when pores are smaller (nanometer). On the contrary, adsorption holds the key role when pores are bigger (micrometer), allowing permeation of molecules in the film volume.

Cation-induced self-assembly of an amphiphilic perylene diimide derivative in solution and Langmuir–Blodgett films

Abstract A novel amphiphilic perylenetetracarboxylic diimide (PDI) derivative, N-(4′-benzo-15-crown-5-ether)-N-hexyl-1,7-di(4-tert-butyl-phenoxy)perylen-3,4,9,10-tetracarboxylic diimide (15C5PDI), has been synthesized and characterized. Dimerization of 15C5PDI is induced in CHCl 3 solution with the present of K + , resulting in the formation of the slipped co-facial J -aggregates, as revealed by absorption and fluorescence spectroscopies. Analysis of the surface pressure–area ( π – A ) isotherms and spectral change for the monolayer formed at the air/water interface, disclosed that 15C5PDI molecules adopted the H -type aggregation mode with a face-to-face configuration and edge-on orientati…

Humidity Insensitive Conductometric Sensors for Ammonia Sensing

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 sens…

Electrical transduction in phthalocyanine-based gas sensors: from classical chemiresistors to new functional structures

Phthalocyanines are organic-based materials which have attracted a lot of research in recent times. In the field of sensors, they present interesting and valuable potentialities as sensing elements for real gas sensor applications. In the present article, and taking some of our experiments as representative examples, we review the different ways of transduction applied to such applications. Some of the new tendencies and transducers for gas sensing based on phthalocyanine derivatives are also reported. Among them, electrical transduction (resistors, field-effect transistors, diodes, etc.) has been, historically, the most commonly exploited way for the detection and/or quantification of gas…

Development of microwave gas sensors

Abstract This work presents a novel approach in gas detection by an original method of microwave transduction. The design of the sensor includes a coplanar grounded wave guide with a gas sensing material to study its sensitivity to ammonia in argon flux. The sensing material can play the role of the substrate or can be deposited as a thin layer on a microstrip structure used in electronics. Submitted to an electromagnetic excitation in microwave energies, the sensor response in the presence of a gas results in a specific modification of the reflected wave (real and imaginary parts). The goals of this study include an examination of the form of the sensitive material and its influence on the…

Molecular Engineering of Porphyrin‐Tapes/Phthalocyanine Heterojunctions for a Highly Sensitive Ammonia Sensor

International audience; Modulating the interfacial charge alignments by molecular engineering in an organic heterojunction device is a smart strategy to improve its conductivity, which can be exploited in high performance gas sensors development. Herein, the fabrication of new organic heterojunction devices based on porphyrin tapes and phthalocyanines and their potentiality in ammonia sensing at different relative humidity (rh) are investigated. The devices are built using dry approach relying on oxidative chemical vapor deposition for simultaneous synthesis, doping and deposition of the porphyrin tape layer and physical vapor deposition of phthalocyanine layer. The association of the porph…

A tungsten oxide–lutetium bisphthalocyanine n–p–n heterojunction: from nanomaterials to a new transducer for chemo-sensing

We report on a new hybrid heterojunction gas-sensitive device by combining a molecular material with a metal oxide. WO3 was synthesised via an aerosol-assisted chemical vapour deposition technique from a tungsten hexacarbonyl precursor. Onto an inorganic film, LuPc2 was vacuum evaporated. The morphology of the WO3–LuPc2 hybrid films is dominated by the morphological features of the tungsten oxide film, as shown by scanning electron microscopy and atomic force microscopy. Raman spectroscopy of the device confirms the presence of both materials. The non-linear I–V characteristics demonstrate the existence of an energy barrier at the interface between the inorganic and molecular materials. The…

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…

Proton coupled electron transfer of ubiquinone Q2 incorporated in a self-assembled monolayer.

We present a complete study of the reduction of ubiquinone Q(2) (UQ(2)) in simpler aqueous medium, over a pH range of 2.5 to 12.5. The short isoprenic chain ubiquinones (UQ(2)) were incorporated in a self-assembled monolayer. Under these conditions, the global 2e(-) electrochemical reaction can be described on the basis of a nine-member square scheme. The thermodynamic constants of the system were determined. The global 2e(-) process is controlled by the uptake of the second electron. The elementary electrochemical rate constants obtained by fitting of the experimental rate constant were k(s4) = 1.5 s(-1) for QH˙(+)(2)↔ QH(2), k(s5) = 1.5 s(-1) for QH˙↔ QH(-) and k(s6) = 1 s(-1) for Q˙(-)↔ …

Alkylthio-tetrasubstituted μ-Nitrido Diiron Phthalocyanines: Spectroelectrochemistry, Electrical Properties, and Heterojunctions for Ammonia Sensing.

Alkylthio-tetrasubstituted μ-nitrido diiron phthalocyanine complexes are synthesized with n-butyl, iso-butyl, tert-butyl, and n-hexadecyl alkyl moieties. For the first time, a spectroelectrochemical investigation of μ-nitrido diiron phthalocyanines is achieved at all the redox steps. The complexes are stable in all their redox states, unlike their unsubstituted analogues. The interest of the present complexes is to prepare sensing devices by a solution processing method. Films are characterized by electronic absorption and Raman spectroscopies. Electrical measurements on resistors show the highly resistive behavior of these complexes, whatever the chain length. However, when combined with t…

Series of charge transfer complexes obtained as crystals in a confined environment

A series of charge transfer complexes (CTCs) were successfully formed by solvent free processing techniques, using the 1,2,4,5-tetracyano benzene (TCNB) as πA molecule and a series of p-dihydroquinones (H2Qs) as πD counterparts. Additionally to the classical co-evaporation techniques, we obtained CTCs in less than an hour, in a very simple confined environment, between two 100 μm – spaced glass plates. A systematical study by Raman spectroscopy on crystals highlighted the CTCs formation. Moreover, three new crystalline structures were obtained, namely TCNB-H2Q that crystallizes in columns connected to each other by H-bonds, while with the methoxy- and dimethoxy-H2Qs the CTC forms crystals w…

Self-assembled aggregates of amphiphilic perylene diimide-based semiconductor molecules: effect of morphology on conductivity.

Abstract Two amphiphilic perylenetetracarboxylic diimide derivatives modified with different side chains at imide nitrogen, N- n -hexyl-N′-(2-hydroxyethyl)-1,7-di(4′-t-butyl)phenoxy-perylene-3,4:9,10-tetracarboxylic diimide ( PDI 1 ) and N,N′-di(2-hydroxyethyl)-1,7-di(4′-t-butyl)phenoxy-perylene-3,4:9,10-tetracarboxylic diimide ( PDI 2 ), were fabricated into organic nanostructures via solution-phase self-assembly. Their self-assembling properties in methanol and n -hexane have been comparatively studied by electronic absorption, fluorescence, and Fourier transform infrared spectroscopy (FT-IR). The morphologies and structures of the self-assemblies were examined by scanning electronic micr…

Grafting, self-organization and reactivity of double-decker rare-earth phthalocyanine

Unveiling the interplay of semiconducting organic molecules with their environment, such as inorganic materials or atmospheric gas, is the first step to designing hybrid devices with tailored optical, electronic or magnetic properties. The present article focuses on a double-decker lutetium phthalocyanine known as an intrinsic semiconducting molecule, holding a Lu ion in its center, sandwiched between two phthalocyanine rings. Carrying out experimental investigations by means of electron spectroscopies, X-ray diffraction and scanning probe microscopies together with advanced ab initio computations, allows us to unveil how this molecule interacts with weakly or highly reactive surfaces. Our…

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…

Electrochemical detection of the 2-isobutyl-3-methoxypyrazine model odorant based on odorant-binding proteins: The proof of concept

Abstract We developed an electrochemical assay for the detection of odorant molecules based on a rat odorant-binding protein (rOBP3). We demonstrated that rOBP3 cavity binds 2-methyl-1,4-naphtoquinone (MNQ), an electrochemical probe, as depicted from the decrease of its electrochemical signal, and deduced the dissociation constant, Kd MNQ  = 0.5(± 0.2) μM. The amount of MNQ displaced from rOBP3 by 2-isobutyl-3-methoxypyrazine (IBMP), a model odorant molecule, was measured using square-wave voltammetry. The release of MNQ by competition led to an increase of the electrochemical response. In addition, this method allowed determination of the dissociation constant of rOBP3 for IBMP, Kd IBMP  =…

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…

All-organic device with integrated chemical filter dedicated to the selective measurement of NO2 in air

Abstract An original organic semiconductor gas sensor devoted to the selective monitoring of nitrogen dioxide in air has been successfully developed. This device combines the great sensitivity and the partial selectivity toward oxidizing gases of a molecular organic semiconductor, copper phthalocyanine, with the O3 filtering selectivity of an organic material, indigo. Experimental measurements highlight filtering yield of indigo close to 100% toward O3 and lower than 10% for NO2. Nanometric indigo layers were realized for the first time by thermal evaporation and characterized by FT-IR spectroscopy. Such all-organic device exhibits a high NO2 sensitivity for low concentrations, a resolution…

A Ubiquinol-Based Charge-Transfer Complex Obtained from a Solvent-Free Approach

Hybrid and 2D nanomaterials

International audience; In order to still improve the performances of chemical sensors, numerous hybrid materials were synthesized that combined at least two types of materials reported in the three previous chapters. We will distinguish materials combining macrocyclic molecules with polymers, those in which these molecules are associated to carbonaceous materials, mainly carbon nanotubes (CNTs) and graphene, and organic-inorganic hybrid materials. In this chapter, we will also include 2D materials introduced recently as sensing materials after the huge development of graphene and graphene oxide-based materials.

Molecular semiconductor-doped insulator (MSDI) heterojunctions as new transducers for chemical sensors

International audience; This article describes a new principle of transduction involving an heterojunction between a Molecular Semiconductor and a Doped Insulator (MSDI). Herein, we report on an MSDI-based sensor featuring an heterojunction between a lutetium bisphthalocyanine (LuPc), which acts as Molecular Semiconductor (MS) and a thin film of Doped Insulator (DI) made of substituted or fluorinated copper phthalocyanine (CuFPc, where = 0, 8, 16). Previously, we reported the peculiar effect of the heterojunction on the MSDI's electronic behavior, suggesting this device as a new kind of transducer for gas chemosensing. Indeed, of particular significance was the key role of modulator played …

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…

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…

Microwave-based gas sensor with phthalocyanine film at room temperature

Abstract This work presents the development of a microwave gas sensor at room temperature. The design of the sensor includes a coplanar grounded wave guide where is deposited a molecular gas sensing material. In this study, the sensitive material is a thin layer of cobalt phthalocyanine (CoPc), sensitive to ammonia and toluene. Submitted to an electromagnetic incident wave in the microwave range, the sensor response is a reflected wave. In the presence of pollutant, the reflected wave shape is specific to the species concentrations. The results interpretation is led at each frequency by the evaluation of the reflected coefficient, which traduces the ratio between the reflected wave over the…

Modulating the Electrical Properties of Organic Heterojunction Devices Based On Phthalocyanines for Ambipolar Sensors.

International audience; HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

The lower rather than higher density charge carrier determines the NH 3 -sensing nature and sensitivity of ambipolar organic semiconductors

International audience; Despite the extensive studies and great application potentials, the sensing nature of ambipolar organic semiconductor gas sensors still remains unclarified, unlike their inorganic counterparts. Herein, different numbers of thiophenoxy groups are introduced into the phthalocyanine periphery of bis(phthalocyaninato) rare earth semiconductors to continuously tune their HOMO and LUMO energies, resulting in the ambipolar M[Pc(SPh)(8)](2) [M = Eu (1), Ho (2)] and p-type M(Pc)[Pc(SPh)(8)] [M = Eu (3), Ho (4)]. An OFET in combination with direct I-V measurements over the devices from the self-assembled nanostructures of 1-4 revealed the original electron and hole densities (…

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…

New Quadratic Self-Assembly of Double-Decker Phthalocyanine on Gold(111) Surface : From Macroscopic to Microscopic Scale

Unveiling the self-organization mechanism of semiconducting organic molecules onto metallic surfaces is the first step to design hybrid devices in which the self-assembling is exploited to tailor magnetic properties. In this study, double-decker rare-earth phthalocyanines, namely, lutetium phthalocyanine (LuPc2), are deposited on Au(111) gold surface forming large-scale self-assemblies. Global and local experimental techniques, namely, grazing incidence X-ray diffraction and scanning tunneling microscopy, supplemented by density functional theory calculations with van der Waals corrections, give insight into the molecular structural arrangement of the thin film and the self organization at …

Elaboration of ammonia gas sensors based on electrodeposited polypyrrole - cobalt phthalocyanine hybrid films

The electrochemical incorporation of a sulfonated cobalt phthalocyanine (sCoPc) in conducting polypyrrole (PPy) was done, in the presence or absence of LiClO4, in order to use the resulting hybrid material for the sensing of ammonia. After electrochemical deposition, the morphological features and structural properties of polypyrrole/phthalocyanine hybrid films were investigated and compared to those of polypyrrole films. A gas sensor consisting in platinum microelectrodes arrays was fabricated using silicon microtechnologies, and the polypyrrole and polypyrrole/phthalocyanine films were electrochemically deposited on the platinum microelectrodes arrays of this gas sensor. When exposed to a…

Facile approaches to build ordered amphiphilic tris(phthalocyaninato) europium triple-decker complex thin films and their comparative performances in ozone sensing

Solution processed thin films of an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu(2)[Pc(15C5)(4)](2)[Pc(OC(10)H(21))(8)], have been prepared from three different methods: self-assembly (SA) annealed in solvent vapor, quasi-Langmuir-Shäfer (QLS) and drop casting methods. In particular, we successfully developed a simple QLS process for fabricating ordered multilayers with a good thickness control. The films prepared from three different methods were characterized by a wide range of methods including electronic absorption spectra, IR, X-ray diffraction, atomic force microscopy (AFM), and current-voltage (I-V) measurements. J-type aggregates have been formed with the …

A Novel Gas Sensor Transducer Based on Phthalocyanine Heterojunction Devices

Abstract: Experimental data concerning the changes in the current-voltage (I-V) perfor-mances of a molecular material-based heterojunction consisting of hexadecafluorinated nickel phthalocyanine (Ni(F 16 Pc)) and nickel phthalocyanine (NiPc), (Au|Ni(F 16 Pc)|NiPc|Al) are introduced as an unprecedented principle of transduction for gas sensing performances. The respective n - and p -type doped-insulator behaviors of the respective materials are supported, owing to the observed changes in surface potential (using the Kelvin probe method) after submission to electron donor (ammonia) and electron acceptor gases (ozone). On the other hand, the bilayer device exhibits strong variations in the bui…

Molecular semiconductor-doped insulator (MSDI) heterojunctions: an alternative transducer for gas chemosensing

New organic devices including a heterojunction between a semiconducting molecular material (MS)--lutetium bisphthalocyanine (LuPc2)--and a doped insulator (DI)--copper phthalocyanine (Cu(F(n)Pc), where n = 0, 8, 16)--are designed and studied as transducers for redox-active species sensing.

Two-Step Solution-Processed Two-Component Bilayer Phthalocyaninato Copper-Based Heterojunctions with Interesting Ambipolar Organic Transiting and Ethanol-Sensing Properties

International audience; The two-component phthalocyaninato copper-based heterojunctions fabricated from n-type CuPc(COOC8H17)(8) and p-type CuPc(OC8H17)(8) by a facile two-step solution-processing quasi-Langmuir-Shafer method with both n/p- and p/n-bilayer structures are revealed to exhibit typical ambipolar air-stable organic thin-film transistor (OTFT) performance. The p/n-bilayer devices constructed by depositing CuPc(COOC8H17)(8) film on CuPc(OC8H17)(8) sub-layer show superior OTFT performance with hole and electron mobility of 0.11 and 0.02 cm(2) V-1 s(-1), respectively, over the ones with n/p-bilayer heterojunction structure with the hole and electron mobility of 0.03 and 0.016 cm(2) …

Tuning the semiconducting nature of bis(phthalocyaninato) holmium complexes via peripheral substituents

The semiconducting properties of the heteroleptic and homoleptic bis(phthalocyaninato) holmium complexes bearing electron-withdrawing phenoxy substituents at the phthalocyanine periphery, namely Ho(Pc)[Pc(OPh)8] (1) and Ho[Pc(OPh)8]2 (2) [Pc = unsubstituted phthalocyaninate; Pc(OPh)8 = 2,3,9,10,16,17,23,24-octaphenoxyphthalocyaninate] have been investigated comparatively. Using a solution-based Quasi–Langmuir–Shafer (QLS) method, the thin solid films of the two compounds were fabricated. The structure and properties of the thin films were investigated by UV-vis absorption spectra, X-ray diffraction (XRD) and atomic force microscopy (AFM). Experimental results indicated that H-type molecular…

Development of gas sensors by microwave transduction with phthalocyanine film

International audience; This work presents a new transduction mode for gas sensing using a passive microwave circuit at room temperature. The design of the sensor includes a microstrip line where is deposited a thin molecular layer of cobalt phthalocyanine (CoPc). The material is sensitive to ammonia and toluene. Submitted to an electromagnetic incident wave in the microwave range, the sensor response is a reflected wave. In the presence of ammonia, the reflected wave is specific to the species concentration. The sensor response is the reflected wave over the incident wave ratio at each frequency traduced by the reflected coefficient. The study deals with the influence of molecular sensitiv…

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 …

Microstructured electrodeposited polypyrrole–phthalocyanine hybrid material, from morphology to ammonia sensing

Hybrid materials combining polypyrrole with ionic macrocycles as counterions are electrosynthesized at the surface of platinum interdigitated electrodes. The chemical composition of the hybrid films is characterized by infrared reflexion absorption spectroscopy (IRRAS) and glow discharge optical emission spectroscopy (GDOES) and their morphology is studied by a range of techniques such as optical topomicroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The obtained films reveal to be more homogeneous, with smaller crystallites, compared to polypyrrole synthesized with small counterions. Finally, the films exhibit a higher sensitivity to ammonia, with a very good…

Proton Transfer versus Hydrogen Bonding: The Reduction of Ubiquinone Q2Incorporated in a Self-Assembled Monolayer in Unbuffered Aqueous Solution

The electrochemical reduction of ubiquinone Q2 (UQ2) in unbuffered aqueous media was investigated over a pH range of 2 to 11, and the results were compared to those obtained in our previous work in buffered solutions. The short isoprene chains of UQ2 were incorporated in a self-assembled monolayer. Analysis of the mechanism and a study in D2O solutions allowed us to demonstrate the important role of hydrogen bonding in the stabilization of the reduced species, also in water. If the concentration of H+ is low relative to that of the quinone, the electrochemical reaction does not proceed through proton-coupled electron transfer, as it does in buffered medium or at low pH values (pH<4.4). We p…

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…

p -Type and n -type conductometric behaviors of octachloro-metallophthalocyanine-based heterojunctions, the key role of the metal

In the present work, we determined the electrical properties of octachlorinated metallophthalocyanines with Co(II) and Cu(II) ions as metal centers. We engaged them in heterojunctions, with lutetium bisphthalocyanine as a partner. Surprisingly, cobalt and copper complexes show opposite behaviors, the first being an [Formula: see text]-type material whereas the latter is a [Formula: see text]-type material, as deduced from the response of the heterojunctions towards ammonia; showing the unusual key role played by the metal center. While the LuPc[Formula: see text]/Cu(Cl[Formula: see text]Pc) complex exhibits a negative response to ammonia, the LuPc[Formula: see text]/Co(Cl[Formula: see text…

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…

Morphology controlled nano-structures of an octa(phenoxy)-substituted phthalocyaninato zinc complex: solvent effect on the self-assembly behaviour

The 2,3,9,10,16,17,24,25-octakis(phenoxy)phthalocyaninato zinc, (Zn[Pc(OPh)8]) was fabricated into nano-/micro-structures via solution-phase self-assembly. The self-assembling properties of Zn[Pc(OPh)8] in coordinating and non-coordinating solvents (methanol and n-hexane) have been comparatively studied by electronic absorption, fluorescence, Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques. The conducting properties were evaluated by current–voltage (I–V) measurements. Due mainly to the presence of different intermolecular Zn–O coordination interactions between the Zn[Pc(OPh)…

High Tolerance of Double-Decker Phthalocyanine toward Molecular Oxygen

Because organic electronics suffer from degradation-inducing oxidation processes, oxygen-tolerant organic molecules could solve this issue and be integrated to improve the stability of devices during operation. In this work, we investigate how lutetium double-decker phthalocyanine (LuPc2) reacts toward molecular oxygen and we report microscopic details of its interaction with LuPc2 film by combining X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory. Surprisingly, LuPc2 molecules are found to weakly physisorb below 120 K and appear rather inert to molecular oxygen at more elevated temperatures. We are able to draw a micros…

Thin-Film Transistors: Two-Step Solution-Processed Two-Component Bilayer Phthalocyaninato Copper-Based Heterojunctions with Interesting Ambipolar Organic Transiting and Ethanol-Sensing Properties (Adv. Mater. Interfaces 16/2016)

Solution-processed thin films based on sandwich-type mixed (phthalocyaninato)(porphyrinato) europium triple-deckers: Structures and comparative performances in ammonia sensing

The solution-processed thin films of a series of three sandwich-type mixed (phthalocyaninato)(porphyrinato) europium complexes with different numbers of hydroxyl groups at the meso-substituted phenyl groups of porphyrin ligand 1–3 were prepared by a quasi-Langmuir–Shafer (QLS) method. Examination by spectroscopic methods revealed that J-type aggregates have been formed with the increasing degree of order of molecular stacking 1 < 2 < 3 films. The IR and XRD results reveal that, a dimeric supramolecular structure was formed depending mainly on the π–π interaction between the tetrapyrrole cores of neighboring triple-decker molecules, which, as the building blocks, self-assembled into the targ…

A biometic olfactory based biosensor combining electrochemistry and odorant-binding

A biometic olfactory based biosensor combining electrochemistry and odorant-binding. Food Factory 2012

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…

When the Grafting of Double Decker Phthalocyanines on Si(100)-2 × 1 Partly Affects the Molecular Electronic Structure

International audience; A combined X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and density functional theory (DFT) study has been performed to characterize the adsorbate interaction of lutetium biphthalocyanine (LuPc2) molecules on the Si(100)-2 × 1 surface. Large molecule–substrate adsorption energies are computed and are found to compete with the molecule–molecule interactions of the double decker molecules. A particularly good matching between STM images and computed ones confirms the deformation of the molecule upon the absorption process. The comparison between DFT calculations and XP spectra reveals that the electronic distribution in the two plateaus …

Enhanced chemosensing of ammonia based on the novel molecular semiconductor-doped insulator (MSDI) heterojunctions

Abstract A series of new molecular semiconductor-doped insulator (MSDI) heterojunctions as conductimetric transducers to NH3 sensing were fabricated based on a novel semiconducting molecular material, an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu2[Pc(15C5)4]2[Pc(OC10H21)8], quasi-Langmuir–Shafer (QLS) film, as a top-layer, and vacuum-deposited and cast film of CuPc as well as copper tetra-tert-butyl phthalocyanine (CuTTBPc) QLS film as a sub-layer, named as MSDIs 1, 2 and 3, respectively. MSDIs 1–3 and respective sub-layers prepared from three different methods were characterized by X-ray diffraction, electronic absorption spectra and current–voltage (I–V) measu…

Molecular Semiconductors &amp;mdash; 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…

Optical Fibre NO2 Sensor Based on Lutetium Bisphthalocyanine in a Mesoporous Silica Matrix

International audience; In this article, we describe a NO2 sensor consisting of a coating based on lutetium bisphthalocyanine (LuPc2) in mesoporous silica. The sensor exploits the absorption spectrum change of this material which strongly and reversibly decreases in contact with NO2. NO2 is measured by following the amplitude change in the reflected spectrum of the coating deposited on the tip of a silica fibre. As diffusion of NO2 in LuPc2 is slow, the response time could be slow. To reduce it, the active molecules are dispersed in a mesoporous silica matrix deposited by a sol-gel process (Evaporation Induced Self Assembly) avoiding the formation of large crystals. Doing so, the response i…

CCDC 1994293: Experimental Crystal Structure Determination

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CCDC 2063384: Experimental Crystal Structure Determination

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CCDC 1994294: Experimental Crystal Structure Determination

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