Abstract: Conducting Polymer Dendrites (CPD) can engrave sophisticated patterns of electrical interconnects in their morphology, networking input with output nodes, from low-voltage spikes and with very minimal amounts of resources: they may unlock in operando man ufacturing functionalities for an electronics framework using metamorphism conjointly with electron transport as part of the information processing. The relationship between their structure and the information transport is still however very unclear and hinders the exploitation of the versatility of their morphologies to store and process electrodynamic information. This study details the evolution of CPD's circuit parameters with their growth and shape. By the means of electrochemical impedance spectro scopy (EIS), multiple distributions of relaxation times (DRT) are evidenced and evolve specifically upon growth. Correlations are established between the dispersive capacitance of dendritic morphologies and their growth duration, independently from exoge nous physical variables, such as distance, multi-component evaporation or aging. Deviation of the anomalous capacitance from the conventional Debye dielectric relaxation can be programmed within the morphology, as the growth controls the dispersion coeff icient of the dendrite's constant-phase elements relaxation. These results suggest that the fading-memory time window of pseudo-capacitive interconnects can practically be conditioned using electrogenerated CPD morphogenesis as an in materio learning mec hanism. This study confirms the perspective of using electrochemistry for unconventional electronics, engraving information with low voltage events in the physics of conducting polymer objects, and storing information in their morphology, accessible by i mpedance spectral analysis.
Baron A., Hernández-Balaguera E., Pecqueur S.*
Abstract: Gas detection technologies are essential tools in maintaining safety and environmental standards across various applications. Through advanced sensors and analytical techniques, these systems aim to quickly detect and classify molecular content in an env ironment, providing valuable insights for early warning and effective response to incidents. In this work, we present the development of miniaturized, multiplexed, and connected electronic nose (e-nose) based on impedance spectroscopy technology. Our pla tform has been tested and optimized to process electrical responses of 15 conductimetric cells, each cell is tuned using a drop-casted conducting polymer poly(3-hexylthiophene) and 14 different triflate salts. The recognition of various solvents vapor (a cetone, methanol, isopropanol, water, ethanol and blends of the last two at various concentrations) relies on a Deep-Convolutional Neural Network based on a back propagation algorithm with two hidden layers of 64 and 32 neurons respectively. The achieved experimental results show an effective classification for the e-nose data to discriminate the alcoholic blends by type and composition, with high classification accuracy (~96%).
Vercoutere E., Kenne S., Morchain C., Pecqueur S., Hafsi B.
Abstract: Advances on System-On-Chip and organic sensors allows the development of miniaturized impedance measurement hardware for gas monitoring in IoT. In this work, we present the development of miniaturized, multiplexed, and connected platform for impedance sp ectroscopy. Designed for online measurements and adapted to wireless network architectures, our platform has been tested and optimized to be used for multi-selective chemical organic sensor nodes. Our designed circuit is built from low cost and low power consumption microelectronics components providing real time acquisition. The proposed system is based on ESP32 Microcontroller enabling the management of an impedance network analyzer AD5933 (Analog Devices, Norwood, MA, USA) through its I2C interface. Our system benefits from two multiplexer components allowing calibration process and the interface of 15 conductimetric sensors with fast acquisition (less than 90 ms per acquisition). The paper describes the microelectronics design, the impedance respon se over time, the measurement's sensitivity and accuracy and the testing of the platform with embedded chemical sensors for gas classification and recognition.
Routier L., Westrelin A., Cerveaux A., Foulon P., Louis G., Horlac'h T., Lmimouni K., Pecqueur S., Hafsi B.
Abstract: Contributions of organic semiconducting materials to electronics are particularly hard to assess: As macromolecular organizations, they have low enthalpy so they can be processed in soft conditions and they have resilience to deformation. However, for th e same reason, they have also broader density of energy states and more instabilities than silicon in ambient. Controlling matter's order at low scale and its properties for as long as possible were always golden standards for microelectronics. Neverthel ess, in a time where brain functioning rises even more as a source of inspiration, shall it still be so? Here are presented clues on how physical property dispersions may be relevant features for information generator nodes to recognize patterns. In a co ntext where the information to recognize is not trivial to physically define, no model can rule sensors' classification a priori. Despite this, broadening the conducting polymer temporal responses in a sensing array allows recognizing dynamical voltage p atterns, or broadening conducting polymer's chemistry in a sensing array enlarges a classifier's perception field to recognize solvent vapors in air. By the nature of property dispersions in regards to the information to recognize, physical variabilities (structural and chemical) can be assets to exploit for pattern recognition and not necessarily drawbacks to bypass for hardware manufacturing. The brain architecture is also transient: a part of the processed information is engraved in its topology, sho wing that a hardware classifier can make use of physical instabilities as part of its programing, by forming new connections in a nodal architecture. Some evidences are also presented here, on how dendritic morphogenesis of a conducting polymer can be a mean to store past voltage experiences in the impedance between nodes in a topology. Very distinct electrochemical features appear in the readout impedance information after growth and these features are to be associated with the shape of a voltage wave inputted on the junction. By the physical implementation of materials' disorder and transience in electronics devices, it is expected that organic semiconductors will integrate essential ingredients in future-emerging information generator nodes beyond s ensors: from embedded random information generating resources to evolving abilities in information classification architectures.
Pecqueur S., Baron A., Scholaert C., Toledo Nauto M., Moustiez P., Routier L., Guérin D., Lmimouni K., Coffinier Y., Hafsi B., Alibart F.
Abstract: Conducting Polymer Dendrites (CPD) are truly inspiring for unconventional electronics that shapes topological circuitries evolving upon an application. Driven by electrochemical processes, an electrochemical impedance rules signal propagation from one no de to another. However, clear models dictating their behavior in an electroactive electrolyte have not been identified yet. In this study, we investigate on CPD in an aqueous electrolyte by impedance spectroscopy to unify their signal transport with an e lectrical model, aiming to define a circuit simulation block to integrate these objects in systems for in materio information processing.
Baron A., Hernández-Balaguera E., Pecqueur S.
Abstract: Advances on System-On-Chip and organic sensors allows the development of miniaturized impedance measurement hardware for gas monitoring in IoT. In this work, we present the development of miniaturized, multiplexed, and connected platform for impedance sp ectroscopy. Designed for online measurements and adapted to wireless network architectures, our platform has been tested and optimized to be used for multi-selective chemical organic sensor nodes. Our designed circuit is built from low cost and low power consumption (250 mW) microelectronics components that achieve long duration operability (5 days and 16 HRS) without compromising on sensor measurement accuracy and precision. We used the well-known impedance network analyzer AD5933 (Analog Devices, Norw ood, MA, USA) chip which can measure a spectrum of impedances in the range 5 Hz to 100 kHz. The proposed system is based on ESP32-C3 Microcontroller enabling the management of the AD5933 through its I2C interface. Our system benefits from two multiplexer components CD74HC4067 allowing calibration process and the interface of 15 conductimetric sensors with real time acquisition (less than 90 ms per acquisition). The system is capable of relaying information through the network for data analysis and stora ge. The paper describes the microelectronics design, the impedance response over time, the measurement's sensitivity and accuracy and the testing of the platform with embedded chemical sensors for gas classification and recognition.
Routier L., Westrelin A., Cerveaux A., Louis G., Horlac'h T., Foulon P., Lmimouni K., Pecqueur S., Hafsi B.*
Abstract: Unlike living organisms, electronics is not metamorphic: devices are mass-produced in series, normalized with well-defined standards, aim at being highly stable during operation and are rebutted with poor recyclability when a better version of themselves can be deployed. Software can also be upgraded on the same hardware with no waste, but not the hardware. In nature, systems grow, evolve, copy, adapt to the environment they sense, scavenge only the least natural resources they need to operate and degra de to biomass. Very often, their degree of intelligence is associated to their plasticity and ability to adapt to an environment, proliferating on a substrate in the harshest conditions.-Today, electrochemistry can be a building block for a field of elec tronics which aims at mimicking natural intelligence by growing electro-conductive topologies as a learning mechanism. Specifically, electropolymerization allows on demand neurogenesis of sensitive inputs with chemospecific semiconductors, and morphogene sis of conducting polymer dendritic topologies. As bottom-up strategy, it is a mask-less patterning technique for microelectrodes and devices with high control of thickness/roughness. Like additive-manufacturing, it consumes only what it needs of the mat erial resources available in an electroactive electrolyte environment, to manufacture semiconductors at various doping levels and bandgaps with no precious mineral and ore, and with low energy consumption manufactured in ambient. Fab-less, dynamic electr opolymerization can be used as in operando mechanism to program the generation of sensing elements, the routing of array of devices, in a way brain cells, micellia or roots grow topologies on specific landscapes to achieve their purpose. In an era where new computing paradigms are needed, with manufacturing methods adopting the most care for the environment, electropolymerization inspires from nature to propose new ways hardware can form and embed new learning functionalities by physically evolving.
Abstract: Advances on System-On-Chip and organic sensors allows the development of miniaturized impedance measurement hardware for gas monitoring in IoT. In this work, we present the development of miniaturized, multiplexed, and connected platform for impedance sp ectroscopy. Designed for online measurements and adapted to wireless network architectures, our platform has been tested and optimized to be used for multi-selective chemical organic sensor nodes. Our designed circuit is built from low cost and low power consumption microelectronics components providing real time acquisition. The proposed system is based on ESP32 Microcontroller enabling the management of an impedance network analyzer AD5933 (Analog Devices, Norwood, MA, USA) through its I2C interface. Our system benefits from two multiplexer components allowing calibration process and the interface of 15 conductimetric sensors with fast acquisition (less than 90 ms per acquisition). The paper describes the microelectronics design, the impedance respon se over time, the measurement's sensitivity and accuracy and the testing of the platform with embedded chemical sensors for gas classification and recognition.
Routier L., Westrelin A., Cerveaux A., Foulon P., Louis G., Horlac'h T., Lmimouni K., Pecqueur S., Hafsi B.*
Abstract: CLD (Chlordecone) is a persistent organic pollutant (POP) of great concerns due toxicity and environmental persistence. To this end, we study organic electrochemical transistors (OECT) featuring biological probes to detect CLD. Here, we report a strategy for immobilizing a D09 VHH receptor, which detects CLD-biot in water. WCA (Water Contact Angle), AFM, XPS and FTIR confirm the successful immobilization of D09 on a surface operating as gate electrode sensitive to the presence of CLD-biot in the transfe r characteristic.
Toledo Nauto M., Le Cacher de Bonneville B., Kanso H., Gourdel M.-E., Reverdy C., Gasse C., Saadi P.-L., Rain J.-C., Pecqueur S., Coffinier Y.
Abstract: In the quest to change the way we envision computing, the ability to create connections in between computing nodes on demand offers the very exciting possibility to explore bottom-up strategies when it comes to thinking the design of electronic devices a nd circuits. Recently, the growth of conductive polymer fibers via electropolymerization (most notably poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), abbreviated as PEDOT:PSS) was employed in the realm of neuromorphic hardware, first as a way to tune the resistance of a connection, and then to perform computing tasks, such as biosignal classification trough reservoir computing, thus establishing the advantages of the method.In this work, we propose to demonstrate that electropolymer ization is a useful tool for the creation of sensors that are able to realize computing tasks in an aqueous environment. By taking advantage of the morphology of the fibers, we show that PEDOT:PSS dendrites can discriminate between different types of vol tage pulses emitted in their vicinity by a local gate electrode, thus performing in materio classification.In addition, we discuss the growth of networks of polymer fibers on 2D substrates. The ability to create structures that cover several microelectro des allows us to study the behavior of the whole system instead of a single dendrite, and it highlights the relationship that relates the morphology of the object and its electrical properties. In particular, we show that dendrites present an asymmetric non-linear behavior due to the volume of polymer that increases the capacitance of the device albeit not participating in conduction. Moreover, because of the ionoelectronic coupling that exists within an electrolyte, two active devices working concomita ntly will influence one another. We demonstrate that it is a blessing for the realization of computing tasks, such as logic, and that it can also be used to program the dendrites into non-volatile conductance states. Therefore, dendritic networks could c onstitute a new building block for non-conventional information processing that fits into the larger framework of brain-inspired computing.
Scholaert C., Janzakova K., Coffinier Y., Pecqueur S., Alibart F.
Abstract: Neuromorphic computing and engineering is capitalizing heavily on the new physical properties offered by nantechnologies to engineer biological processes. At the frontiers in between bio-mimetism and bio-inspiration, various solutions have been proposed for synaptic plasticity or neuronal features based on discrete memory elements, bistable switches or transistors circuits. One missing element that has been missing in the neuromorphic toolbox is the ability to reproduce the complex 3D interconnections o bserved in biological neural networks. Here, we propose to take advantage of bipolar electropolymerization of PEDOT dendritic fibers to reproduce the ability of neural networks to generate complex topologies. The electropolymerization mechanism is used t o realize structural plasticity based on Hebbian-like plasticity rules. We explore how such bottom-up process can find optimal topologies for specific computing tasks. We demonstrate that such optimal topologies results in a drastic reduction of intercon nects for classification and reconstruction tasks, thus offering an interesting option for neural network design.
Alibart F., Janzakova K., Scholaert C., Balafrej I., Kumar A., Drouin D., Rouat J., Pecqueur S., Coffinier Y.
Abstract: In electronics, circuits are predefined for a lifetime. Fabricating always the same with highly stable components is a real advantage for mass production. However when technologies are no longer up to date, electronic devices can only be discarded, poorl y recycled, because they cannot adapt. Living organisms, on the other hand, are constantly evolving. They learn and interact with their environment, and when doing so, brain-neurons or tree-roots grow with appearent disorder but a surprising way to learn to exploit local ressources. The way they branch out can be described as morphogenesis and is the symbol of a natural intelligence, too complex to modelize. While conventional electronics seeks to eliminate disorder and variability, we hypothesize that it is possible to make use of it in a novel electronics that uses electrochemistry to mimic biological processes for adaptation. In this study, we will discuss on morphogenesis of a conducting polymer (PEDOT:PSS) through the AC electropolymerization of E DOT in water. The dendritic objects exhibit various morphologies, differing in their thicknesses and number of branches. Their growth mechanism involves diffusion and electromigration of charged species within the solution. We also present the first resu lts characterizing a connection of those objects in the frequency domain, where various dynamics can be observed due to specific mechanisms at the different interfaces. The electropolymerization of EDOT offers an inexpensive way to grow directed connecti ons with a specific impedance to connect components in a system by voltage activation. It could be used to address the limits of the current electronics in terms of cost and flexibility while taking a form that is closer to what can be found in nature.
Abstract: Identifying relevant machine-learning features for multi-sensing platforms is both an applicative limitation to recognize environments and a necessity to interpret the physical relevance of transducers' complementarity in their information processing. Pa rticularly for long acquisitions, feature extraction must be fully automatized without human intervention and resilient to perturbations without increasing significantly the computational cost of a classifier. In this study, we investigate the relative r esistance and current modulation of a 24-dimensional conductimetric electronic nose, which uses the exponential moving average as a floating reference in a low-cost information descriptor for environment recognition. In particular, we identified that dep ending on the structure of a linear classifier, the 'modema' descriptor is optimized for different material sensing elements' contributions to classify information patterns. The low-pass filtering optimization leads to opposite behaviors between unsuperv ised and supervised learning: the latter one favors longer integration of the reference, allowing to recognize five different classes over 90%, while the first one prefers using the latest events as its reference to cluster patterns by environment nature . Its electronic implementation shall greatly diminish the computational requirements of conductimetric electronic noses for on-board environment recognition without human supervision.
Haj Ammar W., Boujnah A., Baron A., Boubaker A., Kalboussi A., Lmimouni K., Pecqueur S.*
Abstract: Neuromorphic computing is an exciting and rapidly growing field that aims to create computing systems that can replicate the complex and dynamic behavior of the human brain. Organic electrochemical transistors (OECTs) have emerged as a promising tool for developing such systems due to their unique bioelectronic properties. In this paper, we present a novel approach for signal classification using an OECT array, which exhibits multifunctional bioelectronic functionality similar to neurons and synapses li nked through a global medium. Our approach takes advantage of the intrinsic device variabilities of OECTs to create a reservoir network with variable neuron-time constants and synaptic strengths. We demonstrate the effectiveness of our approach by classi fying surface-electromyogram (sEMG) signals into three hand gesture categories. The OECT array performs efficient signal acquisition by feeding signals through multiple gates and measuring the response to a group of OECTs with a global liquid medium. We compare the performance of our approach with and without projecting the input on OECTs and observe a significant increase in classification accuracy from 40% to 68%. We also examined how the classification performance is affected by different selection s trategies and numbers of OECTs used. Finally, we developed a spiking neural network-based simulation that mimics the OECTs array and found that OECT-based classification is comparable to the spiking neural network-based approach. Our work paves the way f or the next generation of low-power, real-time, and intelligent biomedical sensing systems.
Ghazal M., Kumar A.*, Garg N., Pecqueur S., Alibart F.*
Abstract: Neural networks are powerful tools for solving complex problems, but finding the right network topology for a given task remains an open question. Biology uses neurogenesis and structural plasticity to solve this problem. Advanced neural network algorith ms are mostly relying on synaptic plasticity and learning. The main limitation in reconciling these two approaches is the lack of a viable hardware solution that could reproduce the bottom-up development of biological neural networks. Here, we show how t he dendritic growth of PEDOT:PSS-based fibers through AC electropolymerization can implement structural plasticity during network development. We find that this strategy follows Hebbian principles and is able to define topologies that leverage better com puting performances with sparse synaptic connectivity for solving non-trivial tasks. This approach is validated in software simulation, and offers up to 61% better network sparsity on classification and 50% in signal reconstruction tasks.
Janzakova K., Balafrej I., Kumar A., Garg N., Scholaert C., Rouat J., Drouin D., Coffinier Y., Pecqueur S., Alibart F.*
Abstract: Multivariate data analysis and machine-learning classification become popular tools to extract features without physical models for complex environments recognition. For electronic noses, time sampling over multiple sensing elements must be a fair compro mise between a period sufficiently long to output a meaningful information pattern, and sufficiently short to minimize training time for practical applications. Particularly when reactivity's kinetic differs from thermodynamic in sensitive materials, fin ding the best compromise to get the most from data is not obvious. Here, we investigate on the influence of data acquisition to improve or alter data clustering for molecular recognition on a conducting polymer electronic nose. We found out that waiting for sensing elements to reach their steady state is not required for classification, and that reducing data acquisition down to the first dynamical information suffice to recognize molecular gases by principal component analysis with the same materials. Especially for online inference, this study shows that a good sensing array is no array of good sensors, and that new figure-of-merits shall be defined for sensing hardware aiming machine-learning pattern-recognition rather than metrology.
Haj Ammar W., Boujnah A., Boubaker A., Kalboussi A., Lmimouni K., Pecqueur S.*
Abstract: In the quest to change the way we envision computing, the ability to create connections in between computing nodes on demand offers the very exciting possibility to explore bottom-up strategies when it comes to thinking the design of electronic devices a nd circuits. Recently, the growth of conductive polymer fibers via electropolymerization (most notably poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), abbreviated as PEDOT:PSS) was employed in the realm of neuromorphic hardware, first as a way to tune the resistance of a connection, and then to perform computing tasks, such as biosignal classification trough reservoir computing, thus establishing the advantages of the method. In this work, we propose to demonstrate that electropolyme rization is a useful tool for the creation of sensors that are able to realize computing tasks in an aqueous environment. By taking advantage of the morphology of the fibers, we show that PEDOT:PSS dendrites can discriminate between different types of vo ltage pulses emitted in their vicinity by a local gate electrode, thus performing in materio classification. In addition, we discuss the growth of networks of polymer fibers on 2D substrates. The ability to create structures that cover several microelect rodes allows us to study the behavior of the whole system instead of a single dendrite. Complex interactions through iono-electronic coupling arise when several fibers are interconnected. These mechanisms (e.g. self- / inter-gating, ionic relaxation,...) offer new possibilities for computing signals and could potentially open the way for new applications.
Scholaert C., Janzakova K., Coffinier Y., Pecqueur S., Alibart F.
Abstract: Microelectrode Arrays (MEAs) are popular tools for in vitro extracellular recording. They are often optimized by surface engineering to improve affinity with neurons and guarantee higher recording quality and stability. Recently, PEDOT:PSS has been used to coat microelectrodes due to its good biocompatibility and low impedance, which enhances neural coupling. Herein, we investigate on electro-co-polymerization of EDOT with its triglymated derivative to control valence between monomer units and hydrophil ic functions on a conducting polymer. Molecular packing, cation complexation, dopant stoichiometry are governed by the glycolation degree of the electro-active coating of the microelectrodes. Optimal monomer ratio allows fine-tuning the material hydrophi licity and biocompatibility without compromising the electrochemical impedance of microelectrodes nor their stability while interfaced with a neural cell culture. After incubation, sensing readout on the modified electrodes shows higher performances with respect to unmodified electropolymerized PEDOT, with higher signal-to-noise ratio (SNR) and higher spike counts on the same neural culture. Reported SNR values are superior to that of state-of-theart PEDOT microelectrodes and close to that of state-of-t he-art 3D microelectrodes, with a reduced fabrication complexity. Thanks to this versatile technique and its impact on the surface chemistry of the microelectrode, we show that electro-co-polymerization trades with manycompound properties to easily gathe r them into single macromolecular structures. Applied on sensor arrays, it holds great potential for the customization of neurosensors to adapt to environmental boundaries and to optimize extracted sensing features.
Ghazal M., Susloparova A., Lefebvre C., Daher Mansour M., Ghodhbane N., Melot A., Scholaert C., Guérin D., Janel S., Barois N., Colin M., Buée L., Yger P., Halliez S., Coffinier Y.*, Pecqueur S.*, Alibart F.
Abstract: Extracting relevant data from real-world experiments is often challenging with intrinsic materials and device property dispersion, such as in organic electronics. However, multivariate data analy-sis can often be a mean to circumvent this and to extract more information when larger datasets are used with learning algorithms instead of physical models. Here, we report on identifying rele-vant information descriptors for organic electrochemical transistors (OECTs) to classify aqueous electrolytes by ionic composition. Applying periodical gate pulses at different voltage magnitudes, we extracted a reduced number of nonredundant descriptors from the rich drain-current dynam-ics, which provide enough information to cluster electrochemical data by principal component analysis between Ca2+-, K+-, and Na+-rich electrolytes. With six current values obtained at the ap-propriate time domain of the device charge/discharge transient, one can identify the cationic iden-tity of a locally probed transient current wit h only a single micrometric device. Applied to OECT-based neural sensors, this analysis demonstrates the capability for a single nonselective de-vice to retrieve the rich ionic identity of neural activity at the scale of each neuron individually when lea rning algorithms are applied to the device physics.
Pecqueur S.*, Vuillaume D., Crljen Ž., Lončarić I., Zlatić V.*
Abstract: Recently, the development of electronic devices to extracellularly record the simultaneous electrical activities of numerous neurons has been blooming, opening new possibilities to interface and decode neuronal activity. In this work, we tested how the u se of EDOT electropolymerization to tune post-fabrication materials could optimize the cell/electrode interface of such devices. Our results showed an improved signal-to-noise ratio, better biocompatibility, and a higher number of neurons detected in com parison with gold electrodes. Then, using such enhanced recordings with 2D neuronal cultures combined with fluorescent optical imaging, we checked the extent to which the positions of the recorded neurons could be estimated solely via their extracellular signatures. Our results showed that assuming neurons behave as monopoles, positions could be estimated with a precision of approximately tens of micrometers.
Ghazal M., Scholaert C., Dumortier C., Lefebvre C., Barois N., Janel S., Çağatay Tarhan M., Colin M., Buée L., Halliez S., Pecqueur S., Coffinier Y., Alibart F.*, Yger P.*
Abstract: This study presents the development of an electronic nose comprising eight homemade sensors with pure P3HT and doped with different materials. The objective is to electronically identify the gases exposed on these sensors and evaluate the accuracy of tar get gas classification. The resistance variation for each sensor is measured over time and the collected data were processed by three different identification techniques as following: principal component analysis (PCA), linear discriminate analysis (LDA) , and nearest neighbor analysis (kNN). The merit factor for the analysis is the relative modulation of the resistance is very important and computationally gives different results. In addition, the fact that we have sensors made with innovative materials where the reproducibility of the response for the same material can be a constraint in the recognition. In contrast, we have shown that despite the lack of reproducibility for the same material on two different sensors and despite the instability during the ten last sec, we have good recognition rates and we can even say which algorithm is better. It is noted that the LDA is the most reliable and efficient method for gas classification with a prediction accuracy equal to 100%, whereas it reach 93.52% a nd 73.14% for PCA and kNN, respectively, for other techniques for 40% of training dataset and 60% of testing dataset.
Boujnah A.*, Boubaker A., Pecqueur S., Lmimouni K., Kalboussi A.
Abstract: The brain capitalizes on the complexity of both its biochemistry for neurons to encode diverse pieces of information with various neurotransmitters and its morphology at multiple cales to route different pathways for neural interconnectivity. Conducting polymer dendrites can show similar features by differentiating between cations and anions thanks to their charge accumulation profile and the asymmetry in their dendriticity that allows projecting spike signals differently. Here, we exploit such mimicry for in materio classification of bursting activity and investigate, in phosphate buffered saline, the capability of such object to sense bursts of voltage pulses of 100 mV amplitude, emitted by a local gate in the vicinity of the dendrite. The dendrite i ntegrates the different activities with a fading memory time window that is characteristic of both the polarity of the spikes and the temporality of the burst. By this first demonstration, the 'material-object' definitely shows great potential to be a no de halfway between the two realms of brain and electronic communication.
Scholaert C., Janzakova K., Coffinier Y., Alibart F., Pecqueur S.*
Abstract: Surface acoustic waves (SAWs) have a broad spectrum of applications, especially in sensing. However, deposition methods of sensitive layers can be controlled locally through electrodeposition unlike other conventional methods, such as drop-casting and at mospheric-pressure plasma. Employing this method, we experimentally demonstrate the local electrodeposition of PEDOT: PSS on a structured active gold surface. We investigate the response of a piezoelectric transducer at 215MHz, by exploiting shear-horizo ntal (SH) surface waves of the ST-cut quartz substrate. The sensor responses were then tested under acetone, methanol, isopropanol and water vapor gases. Phase changes were more observed under water vapors gases. These changes depended on the surface con ductivity of PEDOT: PSS deposited on the sensor. The double-port SAW gas sensors modified with the PEDOT: PSS presented the highest sensitivity in the case of water vapor, with a maximum phase shift of 0.8º and an insertion loss of about 0.5 dB at ro om temperature. The obtained results could pave the way to implement advanced designs of high-performance and wireless electroacoustic gas sensors based on electropolymerization.
Oumekloul Z., Pecqueur S., de Maistre A., Pernod P., Lmimouni K., Talbi A., Hafsi B.
Abstract: During recent years, neuromorphic engineering has gained significant attraction due to its endeavor to reproduce attractive brain features such as high computational efficiency, low power consumption, functional and structural adaptability onto hardware devices for competitive computing development. Currently, most of these implementations are achieved with either standard silicon-based technologies (complementary metal-oxide-semiconductor) or more emerging material and devices (iono-electronic material s and memristor devices). Mainly, these technologies are produced by means of top-down approaches. In contrast, brain computing largely relies on self-assembling processes to interconnect cells and form pathways for neural networks communication. Thus, t o benefit more from neuromorphic features, there is a strong need to explore such devices that can rely on the same bottom-up approach as in the brain. Promising solutions for this question are gathered in organic electronic materials, more precisely in organic mixed ionic electronic conductors. This study is focused on the development of bottom-up fashioned 3D organic devices that are able to mimic biological neural network branching. By employing Alternating-Current (AC) bipolar electropolymerization, we show how one can synthesize polymer dendritic structures and tune its morphologies depending on various applied AC signals . Additionally, we show how dendritic devices may exhibit synaptic plasticity properties (short-term and long-term memory effec t). Finally, we demonstrate implementation of structural plasticity through spike-event activation AC-electropolymerization and the possibility to modify the weight of obtained dendritic connections with respect to spike rate intensity of the applied sig nals.
Janzakova K., Ghazal M., Kumar A., Coffinier Y., Pecqueur S., Alibart F.
Abstract: Over the past few years, organic electronics - and especially organic mixed ionic electronic conductors (OMIECs) - has taken bio sensing and neuromorphic applications to a whole new level. However, one of the major limitations of the mainstream technolog ies today is that electronic circuits need to be pre-shaped according to the intended use and the expected outcome. This top-down approach, far from being flexible/adaptive, does not really make the most of the resources at hand, as it is hard to predict precisely where cells will be located. To counter that, we can either choose to increase the density and the number of electrodes, so that the entire area would be mapped, or shift from a top-down to a bottom-up approach which would allow for a more enl ightened decision-making process. Recently, the electrodeposition of PEDOT:PSS has been explored as a novel technique to grow conducting polymer films and fibers on non-conductive substrates. The work of Janzakova and coworkers took that concept a step f urther by using electropolymerization of EDOT as a way to create freestanding dendritic-like conductive fibers in a 3D environment, paving the way for in operando material modification, and in fine bottom-up fabrication routes that would be more adaptive and allow for more flexibility. Moreover, it was lately showed that these objects could work as Organic Electrochemical Transistors (OECTs). Here, we explore the possibility of growing dendritic-like PEDOT fibers on Multielectrode Arrays (MEAs) via elec tropolymerization of EDOT. Electrophysiological measurements are based on the capacitive coupling between cells and the electrode material. In comparison with local electrodes, the dendritic objects present spatially distributed impedance due to the exte nsions of their dendritic branches interacting with the biological environment. We investigate the relation between morphology and impedance in these dendritic-like fibers by using a non-conventional Electrochemical Impedance Spectroscopy (EIS) setup tha t will allow us to apply a potential difference between the two ends of the dendrites, thus studying how biasing them can affect their behavior. Moreover, it appears that dendritic fibers can be considered both as passive electrodes as well as active dev ices. We explore the use of these two strategies in the context of electrophysiological measurements. Finally, the ability to record biological signals results from the interaction between cells and an electrode. Unconventional objects such as dendrites present spatio-temporal filtering properties that could affect the recording of such signals. We investigate how tuning the impedance of a dendrite might be used to record efficiently bio-signals.
Scholaert C., Janzakova K., Ghazal M., Daher Mansour M., Lefebvre C., Halliez S., Coffinier Y., Pecqueur S., Alibart F.
Abstract: The development of electronic devices such as microelectrode arrays (MEAs), used to record extracellularly simultaneous electrical activity of large populations of neurons is blooming. To enhance the quality of the recordings, the use of electrode made o f conducting polymer such as PEDOT has recently emerged for optimizing the performance of microelectrodes due to its mixed ionic electronic conduction, biocompatibility and low impedance. However, the extent to which these new interfaces can help the alg orithmic pipelines of spike sorting, i.e. turning extracellular potentials into individual spike trains remains unexplored. To address this issue, we checked if the physical positions of the neurons could be reliably inferred from extracellular electrica l recordings obtained by MEAs, and thus be exploited by downstreams spike sorting algorithms. To do so, we combine high resolution images of neuronal tissues and dense recordings performed via high performant electropolymerized electrodes based MEAs. Fir stly, we report the use of EDOT electropolymerization to tune post-fabrication material and geometrical parameters of passive microelectrodes. The process optimizes the cell/electrode interface by decreasing its impedance and improving its affinity with neurons: results demonstrate a better biocompatibility and improved signal-to-noise ratio (SNR) (up to 40 dB). Thanks to the higher SNR, we were able to detect more cells in comparison with gold electrodes from the same neural network by using spike sort ing. Hence, the higher number of cells detected will lead into more accurate analysis of the localization of the active neurons on top of MEA. Secondly, by using these high performant MEAs, we investigated the possibility to accurately estimate the posit ions of the neurons solely from extracellular recordings by studying the correlation between electrical activity (obtained via spike sorting), optical imaging (Fluorescent) and Scanning Electron Microscopy (SEM) of neural networks cultured on MEAs. By us ing the SpykingCircus software to spike sort the extracellular recordings, we estimated the positions of the neurons either by using the center of mass of their electrical signatures, or by inferring the positions assuming cells would behave as monopoles . By superposition of the fluorescent and the SEM images, we compared the observed physical positions of the neurons with the ones predicted by the two aforementioned methods. This approach showed the high accuracy of the monopole hypothesis compared to the center of mass. In this work, we showed how the use of a material engineering technique for optimizing state of art MEAs can enhance the quality of the recordings. Hence, the correlation of these high quality recordings with optical imaging paves the way towards new algorithmic possibilities for spike sorting algorithms that could make use of a more reliable estimation of neuronal positions.
Ghazal M., Scholaert C., Lefebvre C., Barois N., Janel S., Çağatay Tarhan M., Colin M., Buée L., Halliez S., Pecqueur S., Coffinier Y., Alibart F., Yger P.
Abstract: The development of electronic devices for neurosensing is leading to fundamental discoveries in communication setups for interfacing and computing the brain's electrical activity that is still a demanding task in the 21st century. One of the greatest cha llenges for efficient neurosensing is to ensure that detection/transduction between biochemically rich systems and tools is fully mastered to reliably gather relevant information. In extracellular devices such as microelectrode arrays (MEAs), the discord ance lies at the interface between ions and the electrodes. Engineering chemically/morphologically the electrode's materials by decreasing its impedance, improving its affinity with neurons, and boosting its biocompatibility ensures better cell/electrode interface conditions to find the right materials that detect ionic signals from neurons and transduce them into electronic signals with the lowest information loss. Hence, the use of conducting polymers (PEDOT) has emerged for optimizing the performance of microelectrodes in neurosensing due to its mixed ionic electronic conduction, biocompatibility and low impedance. In parallel to the development of passive microelectrode, organic electrochemical transistors (OECTs) have received lots of attention in the biosensing field since they exhibit high coupling with cells and signal amplification. Notably, the transconductance represents an important parameter that depends on geometrical and material parameters that rules largely OECTs performances in biose nsing. In this direction, we explore the use of EDOT electropolymerization to tune post-fabrication material and geometrical parameters of passive microelectrodes for optimizing the cell/electrode interface by decreasing its impedance and improving its a ffinity with neurons (increasing the resistance "Rseal" that represents the cell/electrode cleft). For electropolymerized PEDOT MEAs, we demonstrate long term and stable extracellular recording of primary cortical neurons with a record signal-to-noise ra tio (SNR) up to 37 dB (with ultra-low noise down to 2.1 μV RMS). Secondly, for active sensing with OECTs, this strategy exploits the concept of adaptive sensing where both transconductance and impedance are tuned simultaneously or independently. This approach shows an improvement of OECTs transconductance by 150-percent, volumetric capacitance by 300-percent, and a reduction in array's variability by 60-percent in comparison with standard spin-coated OECTs. The cytotoxicity of the electropolymerized EDOT was assessed for primary neural cells culture and no detrimental effect of electropolymerized EDOT on cell viability was observed. To extract the impedance and transconductance values for both MEAs and OECTs, we combine DC electrical measurements w ith electrochemical impedance spectroscopy (EIS). To show the cell/electrode morphology and neurite outgrowth to electropolymerized microelectrodes, Scanning Electron Microscopy (SEM) was performed. To correlate the morphological changes of the material with the enhancement of its electrical and electrochemical performances, Atomic Force Microscopy (AFM) in liquid and Raman Spectroscopy were achieved. Finally, in-vitro extracellular recorded signals from entorhinal cortex cultured slices and primary cor tical neurons using both MEAs and OECTs are presented. The key novelty of this technique is to propose a post-fabrication material engineering technique that can be used to optimize both passive (MEAs) and active (OECTs) devices for extracellular recordi ng and promote new exploratory sensing strategies to ensure high quality neurosensing alternatives.
Ghazal M., Scholaert C., Daher Mansour M., Janel S., Barois N., Halliez S., Dargent T., Coffinier Y., Pecqueur S., Alibart F.
Abstract: Iono-electronic materials and devices are suscitating lots of interest from both bio-electronics and neuromorphic research communities. In the one hand, iono-electronic materials are offering attractive features such as bio-compatibility, water environme nt operation and efficient ionic to electronic signals transduction. In the other hand, functional devices based on such materials (organic electrochemical transistors, for instance) have shown multiple neuromorphic features from synaptic plasticity to d endritic integration. This talk will present how electropolymerization of PEDOT:PSS materials can be used in both a bio-electronic and a neuromorphic perspective. Electropolymerization of OECT sensors can indeed be advantageously used for optimizing / tu ning the iono-electronic responses of organic electrochemical transistors, thus paving the way to plastic electrophysiological sensors. Notably, we will show how transconductance and volumetric capacitance are evolving with potenstiostatic electropolymer ization. Secondly, bipolar AC electropolymerization can be used to engineer dendritic-like fibers of PEDOT:PSS. Such unconventional structures can implement various neuromorphic concept such as structural plasticity and synaptic plasticity. Finally, comp uting task taking advantage of both electropolymerized sensors and neuromorphic computing will present temporal patterns classification with reservoir computing approach.
Alibart F., Ghazal M., Janzakova K., Kumar A., Scholaert C., Coffinier Y., Pecqueur S.
Abstract: Electropolymerization is a bottom-up materials engineering process of micro/nano-scale that utilizes electrical signals to deposit conducting dendrites morphologies by a redox reaction in the liquid phase. It resembles synaptogenesis in the brain, in whi ch the electrical stimulation in the brain causes the formation of synapses from the cellular neural composites. The strategy has been recently explored for neuromorphic engineering by establishing link between the electrical signals and the dendrites' s hapes. Since the geometry of these structures determines their electrochemical properties, understanding the mechanisms that regulate polymer assembly under electrically programmed conditions is an important aspect. In this manuscript, we simulate this p henomenon using mesoscale simulations, taking into account the important features of spatial-temporal potential mapping based on the time-varying signal, the motion of charged particles in the liquid due to the electric field, and the attachment of parti cles on the electrode. The study helps in visualizing the motion of the charged particles in different electrical conditions, which is not possible to probe experimentally. Consistent with the experiments, the higher AC frequency of electrical activities favors linear wire-like growth, while lower frequency leads to more dense and fractal dendrites' growth, and voltage offset leads to asymmetrical growth. We find that dendrites' shape and growth process systematically depend on particle concentration an d random scattering. We discover that the different dendrites' architectures are associated with different Laplace and diffusion fields, which govern the monomers' trajectory and subsequent dendrites' growth. Such unconventional engineering routes could have a variety of applications from neuromorphic engineering to bottom-up computing strategies.
Kumar A.*, Janzakova K., Coffinier Y., Pecqueur S., Alibart F.
Abstract: Conducting polymers can sense gases, however, it is mostly the dopant that dictates which ones: Here we show that a single conducting polymer discriminates gas-phase water, from ethanol, from acetone, on demand, by varying the nature of its dopant. Seven triflate salts are evaluated as mild to strong p-dopants for poly(3-hexylthiophene) in sensing micro-arrays. Based on the nature of the salts, each material shows a dynamical pattern of polymer conductance modulation that is specific to the exposed solv ent vapors. By multivariate data analysis, we show that the two mildest ones used in an array can be trained to reliably discriminate the three gases, proving that integrating one single conducting polymer suffices to build the input layer of a resistive nose. Moreover, the study points out the existence of tripartite donor-acceptor charge-transfer complexes responsible for chemo-specific molecular sensing. By showing that molecular acceptors have duality to either p-dope and co ordinate volatile electron donors, such behavior can be used to unravel the role of frontier orbital overlapping in organic semiconductors and the formation of charge-transfer complexes in molecular semiconductors.
Boujnah A., Boubaker A., Kalboussi A., Lmimouni K., Pecqueur S.
Abstract: We have adapted a "peel-off" process to structure stacked organic semiconductors (conducting polymers or small molecules) and metal layers for diode microfabrication. The fabricated devices are organic diode rectifier in a coplanar waveguide structure. U nlike conventional lithographic process, this technique does not lead to destroy organic active layers since it does not involve harsh developer or any non-orthogonal solvent that alter the functionality of subsequentially deposited materials. This proce ss also involves recently reported materials, as a p-dopant of an organometallic electron acceptor Copper(II) trifluoromethanesulfonate, that play the role of hole injection layer in order to enhance the performances of the diode. Comparatively to self-a ssembled monolayers based optimized structures, the fabricated diodes show higher reproducibility and stability. High rectification ratio for realized pentacene and poly(3-hexylthiophene) diodes up to 10^6 has been achieved. Their high frequency response has been evaluated by performing theoretical simulations. The results predict operating frequencies of 200 MHz and 50 MHz for pentacene and P3HT diode rectifiers respectively, with an input oscillating voltage of 2 V peak-to-peak, promising for RFID dev ice applications or for GSM band energy harvesting in low-cost IoT objects.
Ferchichi K., Pecqueur S., Guérin D., Bourguiga R., Lmimouni K.
Abstract: Although materials and processes are different from biological cells', brain mimicries led to tremendous achievements in parallel information processing via neuromorphic engineering. Inexistent in electronics, we emulate dendritic morphogenesis by electr opolymerization in water, aiming in operando material modification for hardware learning. Systematic study of applied voltage-pulse parameters details on tuning independently morphological aspects of micrometric dendrites': fractal number, branching degr ee, asymmetry, density or length. Growths time-lapse image processing shows spatial features to be dynamically dependent, and expand distinctively before and after conductive bridging with two electro-generated dendrites. Circuit-element analysis and imp edance spectroscopy confirms their morphological control in temporal windows where growth kinetics is finely perturbed by the input frequency and duty cycle. By the emulation of one's most preponderant mechanisms for brain's long-term memory, its impleme ntation in vicinity of sensing arrays, neural probes or biochips shall greatly optimize computational costs and recognition required to classify high-dimensional patterns from complex environments.
Janzakova K., Kumar A., Ghazal M., Susloparova A., Coffinier Y., Alibart F., Pecqueur S.*
Abstract: Organic electrochemical transistors are considered today as a key technology to interact with a biological medium through their intrinsic ionic-electronic coupling. In this paper, the authors show how this coupling can be finely tuned (in operando) post- microfabrication via the electropolymerization technique. This strategy exploits the concept of adaptive sensing where both transconductance and impedance are tunable and can be modified on-demand to match different sensing requirements. Material investi gation through Raman spectroscopy, atomic force microscopy, and scanning electron microscopy reveals that electropolymerization can lead to a fine control of poly(3,4-ethylenedioxythiophene) (PEDOT) microdomains organization, which directly affects the i ono-electronic properties of organic electrochemical transistors (OECTs). They further highlight how volumetric capacitance and effective mobility of PEDOT:polystyrene sulfonate influence distinctively the transconductance and impedance of OECTs. This ap proach shows to improve the transconductance by 150% while reducing their variability by 60\% in comparison with standard spin-coated OECTs. Finally, they show how the technique can influence voltage spike rate hardware classification with direct interes t in bio-signals sorting applications.
Ghazal M., Daher Mansour M., Scholaert C., Dargent T., Coffinier Y., Pecqueur S.*, Alibart F.*
Abstract: One of the major limitations of standard top-down technologies used in today's neuromorphic engineering is their inability to map the 3D nature of biological brains. Here, it is shown how bipolar electropolymerization can be used to engineer 3D networks of PEDOT:PSS dendritic fibers. By controlling the growth conditions of the electropolymerized material, it is investigated how dendritic fibers can reproduce structural plasticity by creating structures of controllable shape. Gradual topologies evolution is demonstrated in a multielectrode configuration. A detailed electrical characterization of the PEDOT:PSS dendrites is conducted through DC and impedance spectroscopy measurements and it is shown how organic electrochemical transistors (OECT) can be re alized with these structures. These measurements reveal that quasi-static and transient response of OECTs can be adjusted by controlling dendrites' morphologies. The unique properties of organic dendrites are used to demonstrate short-term, long-term, an d structural plasticity, which are essential features required for future neuromorphic hardware development.},
Janzakova K., Ghazal M., Kumar A., Coffinier Y., Pecqueur S.*, Alibart F.*
Abstract: In this work, we demonstrate P3HT (poly 3-hexylthiophene) organic rectifier diode both in rigid and flexible substrate with a rectification ratio up to 106. This performance has been achieved through tuning the work function of gold with a self-assembled monolayer of 2,3,4,5,6-pentafluorobenzenethiol (PFBT). The diode fabricated on flexible paper substrate shows a very good electrical stability under bending tests and the frequency response is estimated at more than 20 MHz which is sufficient for radio frequency identification (RFID) applications. It is also shown that the low operating voltage of this diode can be a real advantage for use in a rectenna for energy harvesting systems. Simulations of the diode structure show that it can be used at GSM an d Wi-Fi frequencies if the diode capacitance is reduced to a few pF and its series resistance to a few hundred ohms. Under these conditions, the DC voltages generated by the rectenna can reach a value up to 1 V.
Ferchichi K.*, Pecqueur S., Guérin D., Bourguiga R., Lmimouni K.
Abstract: Organic semiconductors have enough molecular versatility to feature chemo-specific electrical sensitivity to large families of chemical substituents via different intermolecular bonding modes. This study demonstrates that one single conducting polymer ca n be tuned to either discriminate water-, ethanol- or acetone-vapors, on demand, by changing the nature of its dopant. Seven triflate salts differ from mild to strong p-dopant on poly(3-hexylthiophene) sensing micro-arrays. Each material shows a pattern of conductance modulation for the polymer which is reversible, reproducible, and distinctive of other gas exposures. Based on principal component analysis, an array doped with only two different triflates can be trained to reliably discriminate gases, wh ich re-motivates using conducting polymers as a class of materials for integrated electronic noses. More importantly, this method points out the existence of tripartite donor-acceptor charge-transfer complexes responsible for chemospecific molecular sens ing. By showing that molecular acceptors can have duality to p-dope semiconductors and to coordinate donor gases, such behavior can be used to understand the role of frontier orbital overlapping in organic semiconductors, the formation of charge-transfer complexes via Lewis acid-base adducts in molecular semiconductors.
Boujnah A., Boubaker A., Kalboussi A., Lmimouni K., Pecqueur S.*
Abstract: We have adapted a "peel-off" process to structure stacked organic semiconductors (conducting polymers or small molecules) and metal layers for diode microfabrication. The fabricated devices are organic diode rectifier in a coplanar waveguide structure. U nlike conventional lithographic process, this technique does not lead to destroy organic active layers since it does not involve harsh developer or any non-orthogonal solvent that alter the functionality of subsequentially deposited materials. This proce ss also involves recently reported materials, as a p-dopant of an organometallic electron-acceptor Copper (II) trifluoromethanesulfonate, that play the role of hole injection layer in order to enhance the performances of the diode. Comparatively to self- assembled monolayers based optimized structures, the fabricated diodes show higher reproducibility and stability. High rectification ratio for realized pentacene and poly (3-hexylthiophene) diodes up to 106 has been achieved. Their high frequency respons e has been evaluated by performing theoretical simulations. The results predict operating frequencies of 200 MHz and 50 MHz for pentacene and P3HT diode rectifiers respectively, with an input oscillating voltage of 2 V peak-to-peak, promising for RFID de vice applications or for GSM band energy harvesting in low-cost IoT objects.
Ferchichi K.*, Pecqueur S., Guérin D., Bourguiga R., Lmimouni K.
Abstract: Most of today's strategies to interface biology with electronic hardware are based on layered architectures where the front-end of sensing is optimized separately from the back-end for processing/computing signals. Alternatively, biological systems are c apitalizing on distributed architecture where both sensing and computing are mix together and co-optimized. In this talk, we will present our strategy to implement bio-sensing of electroactive cells in a neuromorphic perspective. We will present how orga nic electrochemical transistors can be used to record electrical signals from neural cells. We will show various strategies capitalizing on the versatility of organic materials synthesis and organic device fabrication to tune and adapt the functionalitie s of such bio-sensors. We will then present how these strategies can be efficiently used to realize computing functions directly at the interface with biology. Notably, we will illustrate how a network of ionic sensors can implement the reservoir computi ng concept, a powerful neuromorphic computing approach of particular interest for dynamical signal processing.
Alibart F., Ghazal M., Janzakova K., Kumar A., Susloparova A., Halliez S., Colin M., Buée L., Guérin D., Dargent T., Coffinier Y., Pecqueur S.
Abstract:
Ghazal M., Daher Mansour M., Halliez S., Coffinier Y., Dargent T., Pecqueur S., Alibart F.
Abstract: Electropolymerization is an interesting bottom-up strategy to structure conducting materials at the micro/nano-scale in liquid phase that offers a wide morphological versatility. Since the geometry of these structures governs their electrochemical proper ties, it is fundamental to decipher the mechanisms that rule the polymer assembling upon the electrically-programmed growth to use this phenomenon as a neuro-inspired building block for unconventional information processing. Herein, we investigate variou s electrical parameters of electropolymerization affecting the conducting polymer network geometry. We find that various structures such as dendrites, trees, fractals as well as low-fractality cables can be obtained between the two-wire electrodes, based on applied voltage amplitude, biasing symmetry, bias frequency, the concentration of monomers and electrode configurations. We qualitatively and quantitatively study the relationship between the electrical parameters affecting geometrical parameters of the conducting polymer network as well as electropolymerization dynamics through video and image processing. The systematic analysis shows that an increase in applied voltage leads to higher growth rate, more branches, and lower surface to bulk ratio. At the other hand, an increase in bias frequency leads to higher growth rate, smaller number of branches, and higher surface to volume ratio. In order to model the experimental phenomena, we simulate a simplified version of the problem with two bipolar met al electrodes and an electrolyte filled with dilute moving particles at random positions, reflecting the monomers in the liquid phase. The wire electrodes are biased with AC frequency and the spacio-temporal potential map is evaluated by solving the Lapl ace equation. The motion of the monomer particles is controlled by the electric field and by random Brownian motion. The particles that happen to touch the electrodes are stuck to the electrodes, with a certain probability of sticking. The stuck particle s are incorporated into the electrode, and the potential is recalculated for the motion of the particles;. The simulations are tested for different AC applied voltages, frequency, duty cycles, and voltage offsets. The increase in applied voltage leads to higher sticking probability; resulting in a higher growth rate, multiple branches, and higher density, which goes well with the experiments. Further, the effect of frequency, which is not so intuitive, shows that higher AC frequency, favors linear cable like growth, while lower frequency leads to more isotropic growth, while voltage offset and non-equal duty cycle lead to asymmetrical growth, in accordance with experiments. In addition, the effect of electrode spacing, different electrode designs, elec trical pulse shapes and the concentration of particles, are also studied. The study helps in visualizing the motion of particles in different electrical conditions, which is not possible to probe experimentally. Some subtle experimental features, such as the effect of preferential growth on the tips, and broadening of the electrode before touching, are observed in the modeling studies. Thus, we find that the different network architectures are associated with different Laplace end diffusion fields gover ning the monomers motion and in turn electropolymerized network geometry. Such unconventional engineering route could have a variety of applications from neuromorphic engineering to bottom-up computing strategies.
Kumar A., Janzakova K., Coffinier Y., Guérin D., Alibart F., Pecqueur S.
Abstract: Most of today's strategies to interface biology with electronic hardware are based on layered architectures where the front-end of sensing is optimized separately from the back-end for processing/computing signals. Alternatively, biological systems are c apitalizing on distributed architecture where both sensing and computing are mix together and co-optimized. In this talk, we will present our strategy to implement bio-sensing of electroactive cells in a neuromorphic perspective. We will present how orga nic electrochemical transistors can be used to record electrical signals from neural cells. We will show various strategies capitalizing on the versatility of organic materials synthesis and organic device fabrication to tune and adapt the functionalitie s of such bio-sensors. We will then present how these strategies can be efficiently used to realize computing functions directly at the interface with biology. Notably, we will illustrate how a network of ionic sensors can implement the reservoir computi ng concept, a powerful neuromorphic computing approach of particular interest for dynamical signal processing.
Alibart F., Ghazal M., Janzakova K., Kumar A., Susloparova A., Halliez S., Colin M., Buée L., Guérin D., Dargent T., Coffinier Y., Pecqueur S.
Abstract: One of the neuromorphic engineering aims is using nanoelectronics' materials and devices to reproduce key features that are used by the brain for computing. Currently, neuromorphic engineering has explored standard silicon-based technologies (i.e. such a s complementary metal-oxide-semiconductor ) or more emerging material and devices (iono-electronic materials and resistive memory devices, for example). Most of these technologies are still bounded to a top down approach. However, brain computing largely rely on bottom-up processes. For instance, interconnectivity between cells and formation of communication pathway in neural networks result principaly from bottom-up organization. Here, we show how dendritic growth of organic conductive polymers (PEDOT) can be used to mimic structural branching observed in neural network. Conducting-polymer based dendritic structures with different morphology are synthesized in a two-electrode setup by pulsed voltage-driven electropolymerization derived from state-of-t he-art bipolar AC-electrochemical synthetic methods. We show how various AC signals can lead to a large variety of dendritic structures and PEDOT morphologies. In a second part, such dendritic structures are used to implement functionnal OECTs. More impo rtantly, we focus on the transconductance and memory effects that can be obtained in such dendritic OECTs such as short tem plasticity. We report on the relationship between dendrites morphologies and STP time constant. This work paves the way to new app roaches for neuromorphic engineering, such as structural plasticity and neural network topology exploration.
Janzakova K., Ghazal M., Kumar A., Coffinier Y., Guérin D., Pecqueur S., Alibart F.
Abstract: Microelectrode arrays (MEAs) are widely used tools for investigating neural activity. To ensure the best sensitivity of the electronic devices to ionic signals and the lowest information loss, their electrochemical interface must be optimized by lowering their surface impedance, with materials that ensure the highest compatibility with the cells at the same time. Here, we show that by the electropolymerization of thiophene-derivatives, functionalized for higher cell biocompatibility and higher electroch emical performances, one can lower the microelectrodes' surface impedance by the control of the polymer morphology. The microelectrode structuring with bottom-up grown conducting polymers was monitored in-situ by voltage-ramped impedance spectroscopy upo n electropolymerization to track its circuit-elements modification. Iterative impedance modeling over the growth confirmed the material's electrochemical dynamic to be controlled by the gradual modifications of specific discrete circuit elements at diffe rent frequency ranges, thanks to the surface electrodes microstructuring. More particularly, we systematically evidenced a monotonic change of the electrode charging from ideal capacitor to constant phase element dominated modes, due to the bulk charging of the conducting polymer. The evolution of the materials morphology screened by atomic force microscopy and electron microscopy has been confronted to the modification of the materials circuit element, and confirmed distinctive charging modes for the e lectrodes that are governed by their different texturing. In addition to the surface morphology, chemical tuning of the electrodeposited polymer has been performed and showed that a fine tuning of the polymer's glycolation promotes the decrease of the el ectrodes' electrochemical impedance down to -15% compared to the unglycolated polymers thanks to a right balance between ionic permeability and electronic performances. Overall, lower impedance values than commercial MEAs have been systematically reached with performances comparable to spin-coated polymer electrodes', and with low performance dispersion over the whole population of electrodes in the MEAs. With the presented preliminary biocompatibility and stability tests, this study aims is to demonstr ate that unusual microfabrication techniques derived from electrochemistry can provide unique features at the material level to match properties of future emerging bioelectronics technologies to the strong requirements of sensing involving biological mat erials with rich material chemistry and morphology. This work paves the way to new approaches for neuromorphic engineering, such as structural plasticity and neural network topology exploration.
Susloparova A., Ghazal M., Guérin D., Halliez S., Coffinier Y., Dargent T., Alibart F., Pecqueur S.
Abstract: The recent progress in the extracellular microelectrode arrays (MEAs) have greatly improved our ability to probe cellular electrophysiological activities. Nevertheless, passive MEAs are subject to small signal-to-noise ratio and small potential detection . Recently, organic electrochemical transistors (OECTs) have been identified as a promising device architecture to improve extracellular potentials recording in electroactive cells culture both in-vitro and in-vivo. In addition to unique properties of in terest for electrophysiology such as biocompatibility, transparency and flexibility, OECTs operating principle is based on the transduction of ionic currents in the biological medium into electronic currents in the organic semiconductor (e.g. PEDOT:PSS) via electrochemical coupling. The transconductance represents an important figure of merit of OECTs and depends on geometrical and material parameters that rules largely OECTs performances for sensing electrophysiological signals. However, as an organic electronic technology, larger device-property distributions are often encountered with respect to the one of metal- or inorganic-based technologies, inherent to the very nature of the soft organic materials involved in the OECTs transduction process. Her e, we explore the possibility to tune post-fabrication material and geometrical parameters of OECTs with electropolymerization of EDOT. We show that this strategy can be used to simultaneously improve OECT transconductance and its geometrical capacitance . The addressed OECT chips were micro-fabricated on a glass substrates with spin coated PEDOT:PSS. Electropolymerization of EDOT on top of spin-coated PEDOT:PSS was carried on with both fix voltage and ramp voltage techniques. A detail impedance analysis was performed during OECTs functionalization. DC electrical characterizations was used to correlate the transconductance and capacitance tuning due to electropolymerization and to assess device performances improvements. Scanning Electron Microscopy (SE M) was used to correlate morphological changes due to electropolymerization with the enhancement in the transconductance and capacitance of the OECTs. Finally, we performed bio-compatibility assessment between primary neural cells culture and the differe nt possible monomers used for electropolymerization to evaluate the possibility to improve affinity between cultured neurons and electropolymerized materials. The key novelty of this material engineering technique is to propose a promising method for tun able OECTs sensors development. For instance, this back-end-of-line tuning technique can reduce chip variability in terms of performance yield and bring OECTs technology to the next maturity level. Furthermore, such flexibility can enable matching the el ectrochemical impedance of the device to the one of the cells, and in the future promote exploratory sensing missions, merging brain-inspired information processing with neuro-sensing.},
Ghazal M., Susloparova A., Halliez S., Colin M., Buée L., Coffinier Y., Pecqueur S., Dargent T., Alibart F.
Abstract: In this study, we present the microfabrication and characterization of a transparent microelectrode array (MEA) system based on PEDOT:PSS for electrophysiology. The influence of the PEDOT:PSS electrode dimensions on the impedance was investigated and the stability over time under physiological environment was demonstrated. A very good transparency value was obtained by our system displaying one of the best impedance and transmittance values when compared to other transparent MEA. After biocompatibility validation, we successfully recorded spontaneous neuronal activity of primary cortical neurons cultured over 4 weeks on the transparent PEDOT:PSS electrodes. This work shows that microelectrodes composed of PEDOT:PSS are very promising as a new tool for both electrophysiology and fluorescence microscopy studies on neuronal cell cultures.
Susloparova A., Halliez S., Begard S., Colin M., Buée L., Pecqueur S., Alibart F., Thomy V., Arscott S., Pallecchi E., Coffinier Y.*
Abstract: Simultaneously optimizing performances, processability and fabrication cost of organic electronic materials is the continual source of compromise hindering the development of disruptive applications. In this work, we identified a strategy to achieve reco rd conductivity values of one of the most benchmarked semiconducting polymers by doping with an entirely solution-processed, water-free and cost-effective technique. High electrical conductivity for poly(3-hexylthiophene) up to 21 S/cm has been achieved, using a commercially available electron acceptor as both a Lewis acid and an oxidizing agent. While we managed water-free solution-processing a three-time higher conductivity for P3HT with a very affordable/available chemical, near-field microscopy reve als the existence of concentration-dependent higher-conductivity micro-domains for which furthermore process optimization might access to even higher performances. In the perpetual quest of reaching higher performances for organic electronics, this work shall greatly unlock applications maturation requiring higher-scale processability and lower fabrication costs concomitant of higher performances and new functionalities, in the current context where understanding the doping mechanism of such class of ma terials remains of the greatest interest.
Ferchichi K., Bourguiga R., Lmimouni K., Pecqueur S.*
Abstract: We report on the comparison between two different driving circuits for addressing micro-fabricated organic electrochemical transistors of different channel resistances and transconductance, aiming for neuromorphic sensing. The Wheatstone bridge configura tion shows interesting results by offering more versatility towards higher resistance materials. However, the Current-Voltage converter observed faster transients. Both circuits show different assets very encouraging for further practical application.
Ghazal M., Dargent T., Pecqueur S., Alibart F.
Abstract: The increasing popularity of machine learning solutions puts increasing restrictions on this field if it is to penetrate more aspects of life. In particular, energy efficiency and speed of operation is crucial, inter alia in portable medical devices. The Reservoir Computing (RC) paradigm poses as a solution to these issues through foundation of its operation - the reservoir of states. Adequate separation of input information translated into the internal state of the reservoir - whose connections do not need to be trained - allow to simplify the readout layer thus significantly accelerating the operation of the system. In this paper, the theoretical basis of RC was first described, followed by a description of its individual variants, their development and state-of-the-art applications in chemical sensing and metrology: detection of impedance changes and ion sensing. Presented results indicate applicability of reservoir computing for sensing and validating the SWEET algorithm experimentally.
Przyczyna D., Pecqueur S., Vuillaume D., Szaciłowski K.*
Abstract:
Ferchichi K., Pecqueur S., Guérin D., Bourguiga R., Lmimouni K.
Abstract: Organic electrochemical transistors (OECTs) offer a powerful functionality for both sensing and neuro-inspired electronics with still much to understand on their time-dependent behavior. OECTs based on PEDOT:PSS conducting polymer h ave revealed two distinctive operation regimes of a device: a low frequency and a higher frequency regimes dominated by the conductance of the polymer and of the gating electrolyte, respectively. However, the systematically observed non-idealities in t he impedance spectra over the large frequency range and ionic concentrations caused by both the materials and the device complexity cannot be explained by simple models. We report on modeling of OECTs by an optimized equivalent circuit model that takes into account the frequency dependence of the device impedance from 1 Hz to 1 MHz for a large ionic concentration range (10-4 - 1 M) and various chemical nature of the ions. Based on experimental data for KCl(aq) and CaCl2(aq). the model explains the time dependency of the OECT as a whole and discusses the sensibility of new introduced elements pseudo-capacitance and inductance to concentration and voltage to understand the local physics. In particular, the observed concentrat ion-dependent negative phase change in the impedance suggests an inductive contribution to the device impedance due to the doping/dedoping process in the organic layer driven by the applied harmonic voltage as an underlying mechanism . The introduction of these non-redundant elements and the study of their behaviors as function of ionic concentration and applied voltage give a more detailed picture of the OECT working principles at a specific time domains which are highly relevant for multi-parametric ion sensing and neuromorphic computing.
Pecqueur S., Lončarić I., Zlatić V., Vuillaume D., Crljen Ž.
Abstract: In the recent years, the organic electrochemical transistors (OECT) have attracted considerable attention for biosensing applications due to the biocompatibility of their materials and their low operating voltages. Upon exposure to an electrolyte, the dr ain current becomes ion-dependent. This can be exploited for sensing ion applications. To facilitate the process of designing such powerful ion sensing devices one needs the ability to simulate the transient dynamical behavior of many OECT elements conne cted in a network. We have developed a generic theoretical model of the OECT element that can be used for such purposes. Our OECT element resembles a typical FET three-port element with the response function parameterized with an additional time-dependen t variable, T, which describes how far the element operates from the stationary state. We have constructed a dynamical equation that describes how T changes in time when the element is exposed to arbitrary external voltages. This makes the element model highly interoperable with generic electrical circuit simulators. We provide an example of possible numerical implementation using the modified nodal analysis. We tested the underlying theoretical assumptions by comparing model predictions with experiment al data and found a reasonable agreement. Our model describes the typical current spikes observed in the literature.
Athanasiou V.*, Pecqueur S., Vuillaume D., Konkoli Z.*
Abstract: Organic electrochemical transistors offer powerful functionalities for biosensors and neuro-inspired electronics, with still much to understand on the time-dependent behavior of this electrochemical device. Here, we report on distributed-element modeling of the impedance of such micro-fabricated device, systematically performed under a large concentration variation for KCl(aq) and CaCl2(aq). We propose a new model which takes into account three main deviations to ideality, that wer e systematically observed, caused by both the materials and the device complexity, over large frequency range (1 Hz-1 MHz). More than introducing more freedom degree, the introduction of these non-redundant parameters and the study of their behaviors as function of the electrolyte concentration and applied voltage give a more detailed picture of the OECT working principles. This optimized model can be further useful for improving OECT performances in many applications (e.g. biosensors, neuro-inspired de vices, ...) and circuit simulations.
Pecqueur S.*, Lončarić I., Zlatić V., Vuillaume D., Crljen Ž.*
Abstract: Neuromorphic computing proposes to process information inspiring from the brain mechanisms to aim computationally cost-effective and intuitive manners to process complex data. While neural network algorithms have proven their real pote ntial in diverse pattern classification applications, their replication into hardware remains technologically challenging. An interesting solution for such hardware implementation is based on organic electrochemical transistors (O ECTs) that have shown promises in emulating synaptic plasticity at the device level, and coherent communication from one device to another. We demonstrate (i) the bottom-up fabrication of OECT micro-arrays and (ii) the pattern classification task using this technology. We achieved the electro-polymerization of a new p-type accumulation-mode conducting polymer, iteratively on top of 12 micrometric OECT devices in a honeycomb array. We characterized the rich material's morphology of the bottom-up grown organic semiconductor structures and assessed their functionality as synaptic transistor devices. The exploitation of the array for the recognition of pulse-frequency-modulated gate-voltage patterns through an aqueous electrolyte show ed that the pattern recognition can cope with the rich variability of device performances, but also that the recognition benefits from the large dispersion in device property of each individual OECTs. These results announce a new game-c hange for organic and molecular electronics. It shows that the chemical and morphological richness of these electronic materials, for which their disorder induces large property distributions, are actually enabling information processing in a neurom orphic computing context: at the image of our brain which exploits in a powerful way the natural morphological and chemical variability of its dendritic and synaptic network.
Pecqueur S., Guérin D., Vuillaume D., Alibart F.
Abstract: Neuromorphic computing and engineering has been the focus of intense research efforts that have been intensified recently by the mutation of Information and Communication Technologies. In fact, new computing solutions and new hardware platforms are expec ted to emerge to answer to the new needs and challenges of our societies. In this revolution, lots of candidates' technologies are explored and will require leveraging of the pros and cons. In this perspective paper belonging to the special issue on neur omorphic engineering of Journal of Applied Physics, we focus on the current achievements in the field of organic electronics and the potentialities and specificities of this research field. We highlight how unique material features available through orga nic materials can be used to engineer useful and promising bio-inspired devices and circuits. We also discuss the opportunities that organic electronics offer for future research directions in the neuromorphic engineering field.
Pecqueur S., Vuillaume D., Alibart F.*
Abstract: Biological computing systems are very inspirational objects, from their structure, organization and up to there computing principles for the development of new computing paradigms. Emulating some of these basic concepts in hardware could potentially revo lutionize our way of processing information. This approach needs to consider the neuromorphic computing paradigm in its globality, from the basic sensors level to the data analysis one. In this presentation, we will put the emphasis on organic materials as a promising platform for future neurmorphic engineering solutions. In particular, we will present an innovative approach that relies on both intrinsic micro-sensors' physics and neuromorphic computing concepts to show pattern classification out of a 1 2-unit bio-sensing array. We adapt the proposition of reservoir computing to demonstrate that relevant computing can be realized based on the ionic dynamics in 400-nm channel-length organic electrochemical transistor (OECT) and the key concept of learnin g. Furthermore, we show that this approach can deal efficiently with the high level of variability obtained by bottom-up electro-polymerized OECT. We discuss the effect of the array size and variability on the performances for a simple real-time classifi cation task paving the way to new sensing and processing approaches.
Pecqueur S., Guérin D., Vuillaume D., Alibart F.
Abstract: Organic diode rectifier have attracted a lot of attention recently for RF energy harvesting, and much effort has been applied toward extending the ultra-high frequency range. An important parameter that should be considered for diodes used in RF rectifie r is the turn on voltage, which should be low to overcome the problem of the low voltage generated and power extracted from energy harvesting. In this work, we focused on pentacene organic rectifier with high rectification ratio and low threshold voltage obtained by tuning the work function of gold with a self-assembled monolayer of PFBT and optimizing the thickness of the organic layer. We demonstrate a high rectification ratio up to 107 and a very low turn on voltage as low as 20 mV. Flexible rectifie r diode have been also fabricated in release paper WO84, high rectification ratio of 106 was obtained even after bending of the device. The pentacene based rectifier diodes were also demonstrated to operate at more than 1GHz. This provides a great potent ial for fabricating high-performance organic flexible diodes and opens the way for the development of high frequency response using organic materials.
Ferchichi K., Pecqueur S., Guérin D., Bourguiga R., Lmimouni K.
Abstract: Based on bottom-up assembly of highly variable neural cells units, the nervous system can reach unequalled level of performances with respect to standard materials and devices used in microelectronic. Reproducing these basic concepts in hardware could po tentially revolutionize materials and device engineering which are used for information processing. Here, an innovative approach that relies on both iono-electronic materials and intrinsic device physics to show pattern classification out of a 12-unit bi osensing array is presented. The reservoir computing and learning concept to demonstrate relevant computing based on the ionic dynamics in 400 nm channel-length organic electrochemical transistor is used. It is shown that this approach copes efficiently with the high level of variability obtained by bottom-up fabrication using a new electropolymerizable polymer, which enables iono-electronic device functionality and material stability in the electrolyte. The effect of the array size and variability on t he performances for a real-time classification task paving the way to new embedded sensing and processing approaches is investigated.
Pecqueur S.*, Mastropasqua Talamo M., Guérin D., Blanchard P., Roncali J., Vuillaume D., Alibart F.*
Abstract: In this work, we propose a strategy to sense quantitatively and specifically cations, out of a single organic electrochemical transistor (OECT) device exposed to an electrolyte. From the systematic study of six different chloride salts over 12 different concentrations, we demonstrate that the impedance of the OECT device is governed by either the channel dedoping at low frequency and the electrolyte gate capacitive coupling at high frequency. Specific cationic signatures, which originates from the diffe rent impact of the cations behavior on the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) polymer and their conductivity in water, allow their discrimination at the same molar concentrations. Dynamic analysis of the device impedance at different frequencies could allow the identification of specific ionic flows which could be of a great use in bioelectronics to further interpret complex mechanisms in biological media such as in the brain.
Pecqueur S.*, Guérin D., Vuillaume D., Alibart F.*
Abstract: In this work, we propose an electrical strategy to extract further more information on an electrolyte cation's nature than its concentration, out of a single organic electrochemical transistor (OECT): a biocompatible device which is nowadays attracting v ery much attention as a sensor platform for bioelectronics. Based on an optimized OECT structure,the systematic study by impedance spectroscopy of 6 different chloride salts over 12 different concentrations demonstrated that the impedance of the OECT dev ice is governed either by electrical or electrolytic transport mechanisms, depending on the frequency range of the study. From both of these ion-dependent impedances, on can extract either the conductance of the electrolytes or the one of the dedoped pol y(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). From the boundaries of both of these very different ion-limited mechanisms, we extracted two uncorrelated ion-dependent output, accessing to information on the electrolyte cation's nature apart from its concentration. This strategy can be implemented in dynamic analysis of complex ionic media, such as for cellular-activity sensing, in order to discriminate cationic flows, without introducing any foreign ion-selective material, which can t hreaten the biocompatibility.
Pecqueur S., Lenfant S., Guérin D., Alibart F., Vuillaume D.
Abstract: The invention relates to an organic electronic component (100) comprising at least one charge generation layer (5) which has an organically p-doped region (5a) that contains a zinc complex as a p-dopant, said zinc complex in turn containing at least one ligand L of the following structure: formula (I) wherein R1 and R2 can be oxygen, sulphur, selenium, NH or NR4 independently from one another, wherein R4 is selected from the group containing alkyl or aryl and which can be bonded to R3; and wherein R3 is selected from the group containing alkyl, long-chain alkyl, cycloalkyl, halogen alkyl, at least partially halogenated long-chain alkyl, halogen cycloalkyl, aryl, arylene, halogen aryl, heteroaryl, heteroarylene, heterocyclic alkylene, heterocycloalkyl, halogen heteroaryl, alkenyl, halogen alkenyl, alkynyl, halogen alkynyl, ketoaryl, halogen ketoaryl, ketoheteroaryl, ketoalkyl, halogen ketoalkyl, ketoalkenyl, halogen ketoalkenyl, halogen alkyl aryl, and halogen alkyl heteroaryl, wherein, for suitable gr oups, one or a number of non-adjacent CH2 groups can be replaced by -O-, -S-, -NH-, -NR°°°-, -SiR°R°°-, -CO-, -COO-, -COR°OR°°-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -O-CS-, -CS-O-, -CY1=CY2 or -C≡C- independently from one another, and in such a way that O and/or S atoms are not directly bonded to one another, and are replaced optionally with aryl- or heteroaryl preferably containing between 1 and 30 C atoms (terminal CH3 groups are understood to be CH2 groups in the sense of CH2-H). The invention further relates to the use of a zinc complex as a p-dopant in charge generation layers.
Kessler F., Maltenberger A., Pecqueur S., Pentlehner D., Regensburger S., Schmid G.
Abstract: We report on hydrazine-sensing organic electrochemical transistors (OECTs) with a design consisting of concentric annular electrodes. The design engineering of these OECTs was motivated by the great potential of using OECT sensing arrays in fields such a s bioelectronics. In this work, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-based OECTs have been studied as aqueous sensors that are specifically sensitive to the lethal hydrazine molecule. These amperometric sensors have many re levant features for the development of hydrazine sensors, such as a sensitivity down to 10-5 M of hydrazine in water, an order of magnitude higher selectivity for hydrazine than for nine other water-soluble common analytes, the capability to e ntirely recover its base signal after water flushing, and a very low operation voltage. The specificity for hydrazine to be sensed by our OECTs is caused by its catalytic oxidation at the gate electrode, and enables an increase in the output current modu lation of the devices. This has permitted the device-geometry study of the whole series of 80 micrometric OECT devices with sub-20-nm PEDOT:PSS layers, channel lengths down to 1 μm, and a specific device geometry of coplanar and concentric electrodes . The numerous geometries unravel new aspects of the OECT mechanisms governing the electrochemical sensing behaviours of the device - more particularly the effect of the contacts which are inherent at the micro-scale. By lowering the device cross-talk, m icrometric gate-integrated radial OECTs shall contribute to the diminishing of the readout invasiveness and therefore further promote the development of OECT biosensors.
Pecqueur S.*, Lenfant S., Guérin D., Alibart F., Vuillaume D.
Abstract: The present invention relates to n-dopants for increasing the electronic conductivity of organic electrical layers, wherein the n-dopant is selected from the group comprising heterocyclic alkali metal salts of the following formula I where X1 - X5 are in dependently selected from the group comprising -CH2-, -CHR-, -CR2-, -C(=O)-, - (C=S) -, - (C=CR2) -, - C(CR)-, =CH-, =CR-, -NH-, -NR-, =N-, -O-, -S-, -Se-, -P(H)-, -P(R)-, -N--, =C--, -CH--, -CR--, -P--, where at least on e Xi provides a heteroatom in the five-membered ring and the ring is formally negatively charged; R is independently selected from the group comprising -H, -D, halogen, -CN, -NO2, -OH, amine, ether, thioether, ester, amide, C1-C50 alkyl, cycloalkyl, acryloyl, vinyl, allyl, aromatic system, fused aromatic system, heteroaromatic system; M = alkali metal or alkaline earth metal and n = 1 or 2.
Kessler F., Pecqueur S., Schmid G.
Abstract: We report on hydrazine-sensing organic electrochemical transistors (OECTs) with a design consisting in concentric annular electrodes. The design engineering of these OECTs was motivated by the great potential of using OECT sensing arrays in fields such a s bioelectronics. In this work, PEDOT:PSS-based OECTs have been studied as aqueous sensors, specifically sensitive to the lethal hydrazine molecule. These amperometric sensors have many relevant features for the development of hydrazine sensors, such as a sensitivity down to 10-5 M of hydrazine in water, an order of magnitude higher selectivity for hydrazine than for 9 other water soluble common analytes, the capability to recover entirely its base signal after water flushing and a very low v oltage operation. The specificity for hydrazine to be sensed by our OECTs is caused by its catalytic oxidation at the gate electrode and enables increasing the output current modulation of the devices. This has permitted the device-geometry study of the whole series of 80 micrometric OECT devices with sub-20-nm PEDOT:PSS layers, channel lengths down to 1 μm and a specific device geometry of coplanar and concentric electrodes. The numerous geometries unravel new aspects of the OECT mechanisms governi ng the electrochemical sensing behaviours of the device, more particularly the effect of the contacts which are inherent at the micro-scale. By lowering the device cross-talking, micrometric gate-integrated radial OECTs shall contribute to the diminishin g of the readout invasiveness and therefore promotes further the development of OECT biosensors.
Pecqueur S., Lenfant S., Guérin D., Alibart F., Vuillaume D.
Abstract: The invention relates to an n-dopant for doping organic electron transport materials, wherein the n-dopant comprises at least one proazaphosphatrane compound having a three times N-substituted phosphorous atom according to formula 1, wherein R1 - R3 are selected independently from each other from the group R comprising H, D, C1-C60 saturated or unsaturated alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, C1-C60 aryl, alkylaryl, heteroaryl, ether, ester and PR'3, wherein the group R' comprises substitutes of the group R without PR'3, wherein R1 - R3 can be bridged independently from each other; X1 -X3 are selected independently from each other from the group comprising a compound and substituted or non-substi tuted C1-C10 alkyl, cycloalkyl, aryl and alkylaryl.
Kessler F., Pecqueur S., Schmid G.
Abstract: Ten new efficient p-dopants for conductivity doping of organic semiconductors for OLEDs are identified. The key advantage of the electrophilic tris(carboxylato) bismuth(III) compounds is the unique low absorption of the resulting doped layers which promo tes the efficiency of OLED devices. The combination of these features with their low fabrication cost, volatility, and stability, make these materials very attractive as dopants in organic electronics.
Pecqueur S., Maltenberger A., Petrukhina M. A., Halik M., Jaeger A., Pentlehner D., Schmid G.*
Abstract: The invention relates to an organic electronic component having a matrix containing a zinc complex as a p-dopant, said zinc complex in turn containing at least one ligand L of the following structure: formula (I) wherein R1 and R2 can be oxygen, sulphur, selenium, NH or NR4 independently from one another, wherein R4 is selected from the group containing alkyl or aryl and which can be bonded to R3, and wherein R3 is selected from the group containing alkyl, long-chain alkyl, cycloalkyl, halogen-alkyl, ar yl, arylene, halogen-aryl, heteroaryl, heteroarylene, heterocyclic-alkylene, heterocycloalkyl, halogen-heteroaryl, alkenyl, halogen-alkenyl, alkynyl, halogen-alkynyl, ketoaryl, halogen-ketoaryl, ketoheteroaryl, ketoalkyl, halogen-ketoalkyl, ketoalkenyl, halogen-ketoalkenyl, halogen-alkyl-aryl, halogen-alkyl-heteroaryl, wherein, for suitable groups, one or a number of non-adjacent CH2-groups can be replaced by -O-, -S-, -NH-, -NR°°°-, -SiR°R°°-, -CO-, -COO-, -COR°OR °°-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -O-CS-, -CS-O-, -CY1=CY2 or -C≡C- independently from one another, and in such a way that O and/or S atoms are not directly bonded to one another, and are replaced optionally with aryl- o r heteroaryl preferably containing between 1 and 30 C atoms (terminal CH3 -groups are understood to be CH2 -groups in the sense of CH2 -H).
Kessler F., Maltenberger A., Pecqueur S., Regensburger S., Schmid G.
Abstract: The invention relates to a method for producing an organic electronic component, wherein the component comprises at least one organic electronic layer having a matrix, wherein the matrix contains a metal complex as a dopant, which metal complex comprises at least one metal atom M and at least one ligand L bonded to the metal atom M, wherein the ligands L have the following structure independently of each other: wherein E1 and E2 can be oxygen, sulfur, selenium, NH, or NR' independently of each other, wh erein R' is selected from the group containing alkyl or aryl and can be bonded to the substituted benzene ring of the ligand L; and the substituents R1 are selected independently of each other from the group comprising branched or unbranched, fluorinated aliphatic hydrocarbons having 1 to 10 C atoms, wherein n = 1 to 5; and the substituents R2 are selected independently of each other from the group comprising -CN, branched or unbranched aliphatic hydrocarbons having 1 to 10 C atoms, aryl, and heteroaryl , wherein m = 0 to at most 5 - n; wherein the deposition of the dopant of the at least one organic electronic layer occurs by means of gas-phase deposition by use of a source, wherein the source is designed in such a way that the dopant experiences impac ts with at least one wall of the source.
Maltenberger A., Pecqueur S., Regensburger S., Schmid G.
Abstract: The invention relates to a method for producing hole-transporting electrical layers, wherein a functionalized organic matrix compound is reacted with at least one cross-linking reagent on a substrate, higher-molecular-weight compounds thus being formed, wherein the functionalized organic matrix compound corresponds to the following formula 1, wherein L is a bond or is selected from the group comprising substituted or unsubstituted, saturated or unsaturated C1-C50 alkyl, aryl, polye thylene glycol, polyethylene diamine, polyester, polyurethane, or polyvinylidene phenyl chains or mixtures thereof; E1 and E2 can be oxygen, sulfur, selenium, NH, or NE3 independently of each other, wherein E3 is selected from the group compri sing substituted or unsubstituted alkyl or aryl, wherein E3 can be bonded to R; R is selected from the group comprising H, D, C1-C10 alkyl or aryl silyl ester, fluorinated or unfluorinated branched or unbranched C1-C 10 alkyl, aryl, or heteroaryl, and RHTL is the backbone of an organic hole transporter, and the cross-linking reagent comprises at least one metal atom from groups 13-15 and at least one organic ligand.
Maltenberger A., Pecqueur S., Schmid G.
Abstract: Self-Assembled Monolayers (SAMs) on gold were successfully implemented to passivate gold contact organic cell stimulating and sensing transistors. The results show the devices to be greatly insulated from water. This breakthrough is proposed as a technol ogical improvement for bio-stimulation and bio-sensing organic field-effect devices.
Pecqueur S., Borrachero Conejo A. I., Bonetti S., Toffanin S., Generali G., Benfenati V., Muccini M.
Abstract: In this work we report the stimulation of astrocytic calcium signalling using an organic cell sensing and stimulating transistor (O-CST). We demonstrate that astroglial cells can adhere and proliferate on these devices giving us the possibility to stimul ate bioelectrical activity in this type of cells. By the use of a microfluorimetric calcium imaging approach we show that our device is able to evoke an increase in intracellular calcium levels. This research opens a new path in the study of glial cells and their bioelectrical activity.
Borrachero Conejo A. I., Bonetti S., Karges S., Pistone A., Quiroga S. D., Natali M., Grishin I., Pecqueur S., Caprini M., Generali G., Muccini M., Toffanin S., Benfenati V.
Abstract: Astroglial ion channels and calcium signalling play a central role in the physiology and pathophysiology of the Central Nervous System. In this context, increasing efforts are needed to generate innovative tool s for monitoring astrocytes biochemical or bioelectrical activity in vitro and in vivo. Organic field effect devices have a great potential for generating advanced biomedical tools to enable real-time recording and manipulation of communicati on signals between neural cells. We previously reported on transparent Organic Cell Stimulating and Sensing Transistors (O-CSTs) that provide bidirectional stimulation and recording of primary neurons. The transparency of the device also all ows the optical imaging of the modulation of the astroglial calcium signalling bioelectrical activity. Here we explore O-CST functionality to stimulate, evoke and control astroglial calcium signalling and whole cell conductance in primary cultured astrocytes. We found thatprimary astroglial cells can adhere, grow and differentiate on the perylene based field-effect transistor. Furthermore does the organic material preserve astrocytes electrophysiological properties. W e show, that the O-CST provides stimulation and thereby evokes intracellular astrocytic calcium response, which can be determined by calcium imaging. The evoked signal was blocked by carbenoxolone and Ruthenium red, thus suggesting i nvolvement of Connexins and TRPV channels. By means of patch-clamp analyses, we explore the effect of the stimulation on the whole-cell conductance of patched astrocytes. We found that the stimulation lead to an exclusive increase in the inward current that could be prevented by application of Ruthenium Red prior to stimulation. This finding suggests a contribution of the transient receptor potential (TRP) channels, of which TRPV-4 has been shown in former studies to mediate Ca2+ influx in astrocytes. Molecular modelling of field distribution obtained by O-CST is also in agreement with experimental data. Our organic cell stimulating and sensing device paves the way to a new generation of devices for stimulation, manipulation and recording of astroglial cells' bioelectrical activity in vitro.
Karges S., Bonetti S., Borrachero Conejo A. I., Pistone A., Quiroga S. D., Natali M., Grishin I., Pecqueur S., Mercuri F., Caprini M., Generali G., Muccini M., Toffanin S., Benfenati V.
Abstract:
Schmid G., Pecqueur S., Halik M.
Abstract: New classes of conductivity doping materials for organic electrical devices, especially lightemitting diodes, have been identified in this study. Conductivity, mobility and charge-carrier density determination was presented with the example of aluminium tris(8-hydroxyquinolate) n-doping, co-evaporated with caesium orthovanadate, a new n-doping material. The refinement of the calculated conductivity and the verification of charge-carrier density were provided via other independent and published methods. The confirmation certified the accuracy of the obtained values, and the methods were used for the characterisation of further dopants and their doping strength. Struture-property relashionships were carried out from the investigation of doping materials at their chemical level and their electrical behaviour. Systematic p-doping studies of different organometallic Lewis acid complexes in different hole transport materials at different dopant concentrations were performed. First of all, the investigation by the metal centres variation of the three paddlewheel dichromium(II,II)-, dimolybdenum(II,II)- and dirhodium(II,II)-trifluoroacetate complexes exhibited the dependency of the p-doping strength with the electrophilily of the core. A ligand variation stu dy over 10 bismuth(III)-carboxylate complexes demonstrated the electron-withdrawing effect of the ligand to be responsible for the enhancement of the p-doping effect in the complex. The conductivity of different hole transporters, doped with different bi smuth dopants, was correlated to the change of dipole moment, pKa and Hammett parameter of the carboxylic acid ligands. From these correlations, Linear Free-Energy Relationships showed the donor/acceptor interaction between the dopant and the semiconduct or to obey a Lewis acid/base equilibrium (hybrid charge-transfer complex formation) rather than on a redox equilibrium (integer charge-transfer complex formation). One of the p-dopants was chosen as replacement in thick hole transport layer of white orga nic light-emitting diodes and showed comparable or better effects on the devices than a reference, doped with a commercially available p-dopant. It demonstrates the potential use of these Lewis acidic p-dopants for other opto-electronic applications in a n organic semiconductor based devices.
Abstract: The invention relates to a bi- or polynuclear metal complex of a metal of groups Vb/VIb/VIIb, or rather groups 5-7, having at least one ligand of the structure (a), wherein R1 and R2, independently of each other, can be oxygen, sulfur, selenium, NH, or N R4, wherein R4 is selected from the group containing alkyl or aryl and can be bonded to R3; and R3 is selected from the group containing alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, haloalkyl, aryl, arylenes, haloaryl, heteroaryl, hete roarylenes, heterocycloalkylenes, heterocycloalkyl, haloheteroaryl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, ketoaryl, haloketoaryl, ketoheteroaryl, ketoalkyl, haloketoalkyl, ketoalkenyl, haloketoalkenyl, wherein for suitable residues, one or more non -adjacent CH2 groups can be replaced, independently of each other, with -O-, -S-, -NH-, -NR°-, -SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2, or -C≡C- in such a way that O and/or S atom s are not bonded directly to each other, likewise optionally are replaced with aryl or heteroaryl preferably containing 1 to 30 C atoms, as a p-type doping agent for matrix materials of electronic components.
Maltenberger A., Pecqueur S., Schmid G., Wemken J. H.
Abstract: The invention relates to an organic electron transport layer n-dopant, the use of said n-dopant to construct organic electronic components, transistors, organic light-emitting diodes, light-emitting electrochemical cells, organic solar cells, photodiodes , and electronic components containing said n-dopant.
Kanitz A., Pecqueur S., Schmid G., Wemken J. H.
Abstract: Organic electronic is up to now the most promising technology in order to realize opto electronic devices suitable on flexible substrates, which can open new markets on plastic-based products. Nevertheless, to compete classic technologies on already exis ting markets, organic electronic needs to improve several of its electrical performances among others. Doping organic semiconductors is one strategy to optimize electrical conductivity on organic materials but is still very limiting compared to inorganic , and understanding the complex mechanism between dopant and organic semiconductor is a prerequisite for their optimization. Even if the experience shows classic dopants to be redox-active chemicals (Cs, Li, O2), the redox activity of some che micals is no prerequisite for doping. Despite its strong reducing property, Cr2(tfa)4 has been demonstrated to be a p-dopant for its Lewis acidity. Cr2(tfa)4 presents an air-sensitivity due to the redox-activit y of the core, which implies that the conception of Lewis acids and bases, stable under oxidizing or reducing conditions,can result in potential air-stable materials which would dope organic semiconductors by the formation of hybrid charge-transfer compl exes.
Pecqueur S., Halik M., Schmid G.
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