Nanoscopic Electrolyte-Gated Vertical Organic Transistors with Low Operation Voltage and Five Orders of Magnitude Switching Range for Neuromorphic Systems.

Electrolyte-gated organic transistors (EGOTs) are promising candidates as a new class of neuromorphic devices in hardware-based artificial neural networks that can outperform their complementary metal oxide semiconductor (CMOS) counterparts regarding processing speed and energy consumption. Several ways in which to implement such networks exist, two prominent methods of which can be implemented by nanoscopic vertical EGOTs, as we show here. First, nanoscopic vertical electrolyte-gated transistors with a donor-acceptor diketopyrrolopyrrole-terthiophene polymer as an active material can be used to reversibly switch the channel conductivity over five orders of magnitude (3.8 nS to 392 µS) and perform switching at low operation voltages down to -1 mV. Second, nanoscopic EGOTs can also mimic fundamental synaptic functions, and we show an interconnection of up to three transistors, highlighting the possibility to emulate biological nerve cells.

Efficient Electronic Tunneling Governs Transport in Conducting Polymer-Insulator Blends.

Electronic transport models for conducting polymers (CPs) and blends focus on the arrangement of conjugated chains, while the contributions of the nominally insulating components to transport are largely ignored. In this work, an archetypal CP blend is used to demonstrate that the chemical structure of the non-conductive component has a substantial effect on charge carrier mobility. Upon diluting a CP with excess insulator, blends with as high as 97.4 wt % insulator can display carrier mobilities comparable to some pure CPs such as polyaniline and low regioregularity P3HT. In this work, we develop a single, multiscale transport model based on the microstructure of the CP blends, which describes the transport properties for all dilutions tested. The results show that the high carrier mobility of primarily insulator blends results from the inclusion of aromatic rings, which facilitate long-range tunneling (up to ca. 3 nm) between isolated CP chains. This tunneling mechanism calls into question the current paradigm used to design CPs, where the solubilizing or ionically conducting component is considered electronically inert. Indeed, optimizing the participation of the nominally insulating component in electronic transport may lead to enhanced electronic mobility and overall better performance in CPs.

Nonequilibrium site distribution governs charge-transfer electroluminescence at disordered organic heterointerfaces.

The interface between electron-donating (D) and electron-accepting (A) materials in organic photovoltaic (OPV) devices is commonly probed by charge-transfer (CT) electroluminescence (EL) measurements to estimate the CT energy, which critically relates to device open-circuit voltage. It is generally assumed that during CT-EL injected charges recombine at close-to-equilibrium energies in their respective density of states (DOS). Here, we explicitly quantify that CT-EL instead originates from higher-energy DOS site distributions significantly above DOS equilibrium energies. To demonstrate this, we have developed a quantitative and experimentally calibrated model for CT-EL at organic D/A heterointerfaces, which simultaneously accounts for the charge transport physics in an energetically disordered DOS and the Franck-Condon broadening. The 0-0 CT-EL transition lineshape is numerically calculated using measured energetic disorder values as input to 3-dimensional kinetic Monte Carlo simulations. We account for vibrational CT-EL overtones by selectively measuring the dominant vibrational phonon-mode energy governing CT luminescence at the D/A interface using fluorescence line-narrowing spectroscopy. Our model numerically reproduces the measured CT-EL spectra and their bias dependence and reveals the higher-lying manifold of DOS sites responsible for CT-EL. Lowest-energy CT states are situated ∼180 to 570 meV below the 0-0 CT-EL transition, enabling photogenerated carrier thermalization to these low-lying DOS sites when the OPV device is operated as a solar cell rather than as a light-emitting diode. Nonequilibrium site distribution rationalizes the experimentally observed weak current-density dependence of CT-EL and poses fundamental questions on reciprocity relations relating light emission to photovoltaic action and regarding minimal attainable photovoltaic energy conversion losses in OPV devices.

A biohybrid synapse with neurotransmitter-mediated plasticity.

Brain-inspired computing paradigms have led to substantial advances in the automation of visual and linguistic tasks by emulating the distributed information processing of biological systems1. The similarity between artificial neural networks (ANNs) and biological systems has inspired ANN implementation in biomedical interfaces including prosthetics2 and brain-machine interfaces3. While promising, these implementations rely on software to run ANN algorithms. Ultimately, it is desirable to build hardware ANNs4,5 that can both directly interface with living tissue and adapt based on biofeedback6,7. The first essential step towards biologically integrated neuromorphic systems is to achieve synaptic conditioning based on biochemical signalling activity. Here, we directly couple an organic neuromorphic device with dopaminergic cells to constitute a biohybrid synapse with neurotransmitter-mediated synaptic plasticity. By mimicking the dopamine recycling machinery of the synaptic cleft, we demonstrate both long-term conditioning and recovery of the synaptic weight, paving the way towards combining artificial neuromorphic systems with biological neural networks.

Organic neuromorphic electronics for sensorimotor integration and learning in robotics.

In living organisms, sensory and motor processes are distributed, locally merged, and capable of forming dynamic sensorimotor associations. We introduce a simple and efficient organic neuromorphic circuit for local sensorimotor merging and processing on a robot that is placed in a maze. While the robot is exposed to external environmental stimuli, visuomotor associations are formed on the adaptable neuromorphic circuit. With this on-chip sensorimotor integration, the robot learns to follow a path to the exit of a maze, while being guided by visually indicated paths. The ease of processability of organic neuromorphic electronics and their unconventional form factors, in combination with education-purpose robotics, showcase a promising approach of an affordable, versatile, and readily accessible platform for exploring, designing, and evaluating behavioral intelligence through decentralized sensorimotor integration.

In situ Parallel Training of Analog Neural Network Using Electrochemical Random-Access Memory.

In-memory computing based on non-volatile resistive memory can significantly improve the energy efficiency of artificial neural networks. However, accurate in situ training has been challenging due to the nonlinear and stochastic switching of the resistive memory elements. One promising analog memory is the electrochemical random-access memory (ECRAM), also known as the redox transistor. Its low write currents and linear switching properties across hundreds of analog states enable accurate and massively parallel updates of a full crossbar array, which yield rapid and energy-efficient training. While simulations predict that ECRAM based neural networks achieve high training accuracy at significantly higher energy efficiency than digital implementations, these predictions have not been experimentally achieved. In this work, we train a 3 × 3 array of ECRAM devices that learns to discriminate several elementary logic gates (AND, OR, NAND). We record the evolution of the network's synaptic weights during parallel in situ (on-line) training, with outer product updates. Due to linear and reproducible device switching characteristics, our crossbar simulations not only accurately simulate the epochs to convergence, but also quantitatively capture the evolution of weights in individual devices. The implementation of the first in situ parallel training together with strong agreement with simulation results provides a significant advance toward developing ECRAM into larger crossbar arrays for artificial neural network accelerators, which could enable orders of magnitude improvements in energy efficiency of deep neural networks.

Buildup of Triplet-State Population in Operating TQ1:PC71BM Devices Does Not Limit Their Performance.

Triplet generation in organic solar cells has been considered a major loss channel. Determining the density of the triplet-state population in an operating device is challenging. Here, we employ transient absorption (TA) spectroscopy on the quinoxaline-thiophene copolymer TQ1 blended with PC71BM, quantify the transient charge and triplet-state densities, and parametrize their generation and recombination dynamics. The charge recombination parameters reproduce the experimentally measured current-voltage characteristics in charge carrier drift-diffusion simulations, and they yield the steady-state charge densities. We demonstrate that triplets are formed by both geminate and nongeminate recombination of charge carriers and decay primarily by triplet-triplet annihilation. Using the charge densities in the rate equations describing triplet-state dynamics, we find that triplet-state densities in devices are in the range of charge carrier densities. Despite this substantial triplet-state buildup, TQ1:PC71BM devices exhibit only moderate geminate recombination and significantly reduced nongeminate charge recombination, with reduction factors between 10-4 and 10-3 compared to Langevin recombination.

Photogenerated Charge Transport in Organic Electronic Materials: Experiments Confirmed by Simulations.

The performance of organic optoelectronic devices, such as organic photovoltaic (OPV) cells, is to a large extent dictated by their ability to transport the photogenerated charge, with relevant processes spanning a wide temporal (fs-µs) and spatial (1-100 nm) range. However, time-resolved techniques can access only a limited temporal window, and often contradict steady-state measurements. Here, commonly employed steady-state and time-resolved techniques are unified over an exceptionally wide temporal range (fs-µs) in a consistent physical picture. Experimental evidence confirmed by numerical simulations shows that, although various techniques probe different time scales, they are mutually consistent as they probe the same physical mechanisms governing charge motion in disordered media-carrier hopping and thermalization in a disorder-broadened density of states (DOS). The generality of this framework is highlighted by time-resolved experimental data obtained on polymer:fullerene, polymer:polymer, and small-molecule blends with varying morphology, including recent experiments revealing that low donor content OPV devices operate by long-range hole tunneling between non-nearest-neighbor molecules. The importance of nonequilibrium processes in organic electronic materials is reviewed, with a particular focus on experimental data and understanding charge transport physics in terms of material DOS.

Equilibrated Charge Carrier Populations Govern Steady-State Nongeminate Recombination in Disordered Organic Solar Cells.

We employed bias-assisted charge extraction techniques to investigate the transient and steady-state recombination of photogenerated charge carriers in complete devices of a disordered polymer-fullerene blend. Charge recombination is shown to be dispersive, with a significant slowdown of the recombination rate over time, consistent with the results from kinetic Monte Carlo simulations. Surprisingly, our experiments reveal little to no contributions from early time recombination of nonequilibrated charge carriers to the steady-state recombination properties. We conclude that energetic relaxation of photogenerated carriers outpaces any significant nongeminate recombination under application-relevant illumination conditions. With equilibrated charges dominating the steady-state recombination, quasi-equilibrium concepts appear suited for describing the open-circuit voltage of organic solar cells despite pronounced energetic disorder.

Parallel programming of an ionic floating-gate memory array for scalable neuromorphic computing.

Neuromorphic computers could overcome efficiency bottlenecks inherent to conventional computing through parallel programming and readout of artificial neural network weights in a crossbar memory array. However, selective and linear weight updates and <10-nanoampere read currents are required for learning that surpasses conventional computing efficiency. We introduce an ionic floating-gate memory array based on a polymer redox transistor connected to a conductive-bridge memory (CBM). Selective and linear programming of a redox transistor array is executed in parallel by overcoming the bridging threshold voltage of the CBMs. Synaptic weight readout with currents <10 nanoamperes is achieved by diluting the conductive polymer with an insulator to decrease the conductance. The redox transistors endure >1 billion write-read operations and support >1-megahertz write-read frequencies.

Design Rule for Improved Open-Circuit Voltage in Binary and Ternary Organic Solar Cells.

Mixing different compounds to improve functionality is one of the pillars of the organic electronics field. Here, the degree to which the charge transport properties of the constituent materials are simply additive when materials are mixed is quantified. It is demonstrated that in bulk heterojunction organic solar cells, hole mobility in the donor phase depends critically on the choice of the acceptor material, which may alter the energetic disorder of the donor. The same holds for electron mobility and disorder in the acceptor. The associated mobility differences can exceed an order of magnitude compared to pristine materials. Quantifying these effects by a state-filling model for the open-circuit voltage (VOC) of ternary Donor:Acceptor1:Acceptor2 (D:A1:A2) organic solar cells leads to a physically transparent description of the surprising, nearly linear tunability of the VOC with the A1:A2 weight ratio. It is predicted that in binary OPV systems, suitably chosen donor and acceptor materials can improve the device power conversion efficiency (PCE) by several percentage points, for example from 11 to 13.5% for a hypothetical state-of-the-art organic solar cell, highlighting the importance of this design rule.

Photo-generated carriers lose energy during extraction from polymer-fullerene solar cells.

In photovoltaic devices, the photo-generated charge carriers are typically assumed to be in thermal equilibrium with the lattice. In conventional materials, this assumption is experimentally justified as carrier thermalization completes before any significant carrier transport has occurred. Here, we demonstrate by unifying time-resolved optical and electrical experiments and Monte Carlo simulations over an exceptionally wide dynamic range that in the case of organic photovoltaic devices, this assumption is invalid. As the photo-generated carriers are transported to the electrodes, a substantial amount of their energy is lost by continuous thermalization in the disorder broadened density of states. Since thermalization occurs downward in energy, carrier motion is boosted by this process, leading to a time-dependent carrier mobility as confirmed by direct experiments. We identify the time and distance scales relevant for carrier extraction and show that the photo-generated carriers are extracted from the operating device before reaching thermal equilibrium.

High-Entropy Mixtures of Pristine Fullerenes for Solution-Processed Transistors and Solar Cells.

The solubility of pristine fullerenes can be enhanced by mixing C60 and C70 due to the associated increase in configurational entropy. This "entropic dissolution" allows the preparation of field-effect transistors with an electron mobility of 1 cm(2) V(-1) s(-1) and polymer solar cells with a highly reproducible power-conversion efficiency of 6%, as well as a thermally stable active layer.

Unified Study of Recombination in Polymer:Fullerene Solar Cells Using Transient Absorption and Charge-Extraction Measurements.

Recombination in the well-performing bulk heterojunction solar cell blend between the conjugated polymer TQ-1 and the substituted fullerene PCBM has been investigated with pump-probe transient absorption and charge extraction of photogenerated carriers (photo-CELIV). Both methods are shown to generate identical and overlapping data under appropriate experimental conditions. The dominant type of recombination is bimolecular with a rate constant of 7 × 10(-12) cm(-3) s(-1). This recombination rate is shown to be fully consistent with solar cell performance. Deviations from an ideal bimolecular recombination process, in this material system only observable at high pump fluences, are explained with a time-dependent charge-carrier mobility, and the implications of such a behavior for device development are discussed.