Photocatalytic doping of organic semiconductors.

Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)1-3 and ultimately enhances device performance4-7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants8-10, which are consumed during the doping process. Achieving efficient doping with weak and/or widely accessible dopants under mild conditions remains a considerable challenge. Here, we report a previously undescribed concept for the photocatalytic doping of OSCs that uses air as a weak oxidant (p-dopant) and operates at room temperature. This is a general approach that can be applied to various OSCs and photocatalysts, yielding electrical conductivities that exceed 3,000 S cm-1. We also demonstrate the successful photocatalytic reduction (n-doping) and simultaneous p-doping and n-doping of OSCs in which the organic salt used to maintain charge neutrality is the only chemical consumed. Our photocatalytic doping method offers great potential for advancing OSC doping and developing next-generation organic electronic devices.

Industrial Kraft Lignin Based Binary Cathode Interface Layer Enables Enhanced Stability in High Efficiency Organic Solar Cells.

Herein, a binary cathode interface layer (CIL) strategy based on the industrial solvent fractionated LignoBoost kraft lignin (KL) is adopted for fabrication of organic solar cells (OSCs). The uniformly distributed phenol moieties in KL enable it to easily form hydrogen bonds with commonly used CIL materials, i.e., bathocuproine (BCP) and PFN-Br, resulting in binary CILs with tunable work function (WF). This work shows that the binary CILs work well in OSCs with large KL ratio compatibility, exhibiting equivalent or even higher efficiency to the traditional CILs in state of art OSCs. In addition, the combination of KL and BCP significantly enhanced OSC stability, owing to KL blocking the reaction between BCP and nonfullerene acceptors (NFAs). This work provides a simple and effective way to achieve high-efficient OSCs with better stability and sustainability by using wood-based materials.

Ground-state electron transfer in all-polymer donor:acceptor blends enables aqueous processing of water-insoluble conjugated polymers.

Water-based conductive inks are vital for the sustainable manufacturing and widespread adoption of organic electronic devices. Traditional methods to produce waterborne conductive polymers involve modifying their backbone with hydrophilic side chains or using surfactants to form and stabilize aqueous nanoparticle dispersions. However, these chemical approaches are not always feasible and can lead to poor material/device performance. Here, we demonstrate that ground-state electron transfer (GSET) between donor and acceptor polymers allows the processing of water-insoluble polymers from water. This approach enables macromolecular charge-transfer salts with 10,000× higher electrical conductivities than pristine polymers, low work function, and excellent thermal/solvent stability. These waterborne conductive films have technological implications for realizing high-performance organic solar cells, with efficiency and stability superior to conventional metal oxide electron transport layers, and organic electrochemical neurons with biorealistic firing frequency. Our findings demonstrate that GSET offers a promising avenue to develop water-based conductive inks for various applications in organic electronics.

Mechanically Adaptive Mixed Ionic-Electronic Conductors Based on a Polar Polythiophene Reinforced with Cellulose Nanofibrils.

Conjugated polymers with oligoether side chains are promising mixed ionic-electronic conductors, but they tend to feature a low glass transition temperature and hence a low elastic modulus, which prevents their use if mechanical robust materials are required. Carboxymethylated cellulose nanofibrils (CNF) are found to be a suitable reinforcing agent for a soft polythiophene with tetraethylene glycol side chains. Dry nanocomposites feature a Young's modulus of more than 400 MPa, which reversibly decreases to 10 MPa or less upon passive swelling through water uptake. The presence of CNF results in a slight decrease in electronic mobility but enhances the ionic mobility and volumetric capacitance, with the latter increasing from 164 to 197 F cm-3 upon the addition of 20 vol % CNF. Overall, organic electrochemical transistors (OECTs) feature a higher switching speed and a transconductance that is independent of the CNF content up to at least 20 vol % CNF. Hence, CNF-reinforced conjugated polymers with oligoether side chains facilitate the design of mechanically adaptive mixed ionic-electronic conductors for wearable electronics and bioelectronics.

Visualisation of individual dopants in a conjugated polymer: sub-nanometre 3D spatial distribution and correlation with electrical properties.

While molecular doping is ubiquitous in all branches of organic electronics, little is known about the spatial distribution of dopants, especially at molecular length scales. Moreover, a homogeneous distribution is often assumed when simulating transport properties of these materials, even though the distribution is expected to be inhomogeneous. In this study, electron tomography is used to determine the position of individual molybdenum dithiolene complexes and their three-dimensional distribution in a semiconducting polymer at the sub-nanometre scale. A heterogeneous distribution is observed, the characteristics of which depend on the dopant concentration. At 5 mol% of the molybdenum dithiolene complex, the majority of the dopant species are present as isolated molecules or small clusters up to five molecules. At 20 mol% dopant concentration and higher, the dopant species form larger nanoclusters with elongated shapes. Even in case of these larger clusters, each individual dopant species is still in contact with the surrounding polymer. The electrical conductivity first strongly increases with dopant concentration and then slightly decreases for the most highly doped samples, even though no large aggregates can be observed. The decreased conductivity is instead attributed to the increased energetic disorder and lower probability of electron transfer that originates from the increased size and size variation in dopant clusters. This study highlights the importance of detailed information concerning the dopant spatial distribution at the sub-nanometre scale in three dimensions within the organic semiconductor host. The information acquired using electron tomography may facilitate more accurate simulations of charge transport in doped organic semiconductors.

Double Doping of a Low-Ionization-Energy Polythiophene with a Molybdenum Dithiolene Complex.

Doping of organic semiconductors is crucial for tuning the charge-carrier density of conjugated polymers. The exchange of more than one electron between a monomeric dopant and an organic semiconductor allows the polaron density to be increased relative to the number of counterions that are introduced into the host matrix. Here, a molybdenum dithiolene complex with a high electron affinity of 5.5 eV is shown to accept two electrons from a polythiophene that has a low ionization energy of 4.7 eV. Double p-doping is consistent with the ability of the monoanion salt of the molybdenum dithiolene complex to dope the polymer. The transfer of two electrons to the neutral dopant was also confirmed by electron paramagnetic resonance spectroscopy since the monoanion, but not the dianion, of the molybdenum dithiolene complex features an unpaired electron. Double doping allowed an ionization efficiency of 200% to be reached, which facilitates the design of strongly doped semiconductors while lessening any counterion-induced disruption of the nanostructure.

Organic electrochemical neurons and synapses with ion mediated spiking.

Future brain-machine interfaces, prosthetics, and intelligent soft robotics will require integrating artificial neuromorphic devices with biological systems. Due to their poor biocompatibility, circuit complexity, low energy efficiency, and operating principles fundamentally different from the ion signal modulation of biology, traditional Silicon-based neuromorphic implementations have limited bio-integration potential. Here, we report the first organic electrochemical neurons (OECNs) with ion-modulated spiking, based on all-printed complementary organic electrochemical transistors. We demonstrate facile bio-integration of OECNs with Venus Flytrap (Dionaea muscipula) to induce lobe closure upon input stimuli. The OECNs can also be integrated with all-printed organic electrochemical synapses (OECSs), exhibiting short-term plasticity with paired-pulse facilitation and long-term plasticity with retention >1000 s, facilitating Hebbian learning. These soft and flexible OECNs operate below 0.6 V and respond to multiple stimuli, defining a new vista for localized artificial neuronal systems possible to integrate with bio-signaling systems of plants, invertebrates, and vertebrates.

Influence of Molecular Weight on the Organic Electrochemical Transistor Performance of Ladder-Type Conjugated Polymers.

Organic electrochemical transistors (OECTs) hold promise for developing a variety of high-performance (bio-)electronic devices/circuits. While OECTs based on p-type semiconductors have achieved tremendous progress in recent years, n-type OECTs still suffer from low performance, hampering the development of power-efficient electronics. Here, it is demonstrated that fine-tuning the molecular weight of the rigid, ladder-type n-type polymer poly(benzimidazobenzophenanthroline) (BBL) by only one order of magnitude (from 4.9 to 51 kDa) enables the development of n-type OECTs with record-high geometry-normalized transconductance (gm,norm  ≈ 11 S cm-1 ) and electron mobility × volumetric capacitance (µC* ≈ 26 F cm-1  V-1 s-1 ), fast temporal response (0.38 ms), and low threshold voltage (0.15 V). This enhancement in OECT performance is ascribed to a more efficient intermolecular charge transport in high-molecular-weight BBL than in the low-molecular-weight counterpart. OECT-based complementary inverters are also demonstrated with record-high voltage gains of up to 100 V V-1 and ultralow power consumption down to 0.32 nW, depending on the supply voltage. These devices are among the best sub-1 V complementary inverters reported to date. These findings demonstrate the importance of molecular weight in optimizing the OECT performance of rigid organic mixed ionic-electronic conductors and open for a new generation of power-efficient organic (bio-)electronic devices.

Tuning of the elastic modulus of a soft polythiophene through molecular doping.

Molecular doping of a polythiophene with oligoethylene glycol side chains is found to strongly modulate not only the electrical but also the mechanical properties of the polymer. An oxidation level of up to 18% results in an electrical conductivity of more than 52 S cm-1 and at the same time significantly enhances the elastic modulus from 8 to more than 200 MPa and toughness from 0.5 to 5.1 MJ m-3. These changes arise because molecular doping strongly influences the glass transition temperature Tg and the degree of π-stacking of the polymer, as indicated by both X-ray diffraction and molecular dynamics simulations. Surprisingly, a comparison of doped materials containing mono- or dianions reveals that - for a comparable oxidation level - the presence of multivalent counterions has little effect on the stiffness. Evidently, molecular doping is a powerful tool that can be used for the design of mechanically robust conducting materials, which may find use within the field of flexible and stretchable electronics.

Electrically Conducting Elastomeric Fibers with High Stretchability and Stability.

Stretchable conducting materials are appealing for the design of unobtrusive wearable electronic devices. Conjugated polymers with oligoethylene glycol side chains are excellent candidate materials owing to their low elastic modulus and good compatibility with polar stretchable polymers. Here, electrically conducting elastomeric blend fibers with high stretchability, wet spun from a blend of a doped polar polythiophene with tetraethylene glycol side chains and a polyurethane are reported. The wet-spinning process is versatile, reproducible, scalable, and produces continuous filaments with a diameter ranging from 30 to 70 µm. The fibers are stretchable up to 480% even after chemical doping with iron(III) p-toluenesulfonate hexahydrate and exhibit an electrical conductivity of up to 7.4 S cm-1 , which represents a record combination of properties for conjugated polymer-based fibers. The fibers remain conductive during elongation until fiber fracture and display excellent long-term stability at ambient conditions. Cyclic stretching up to 50% strain for at least 400 strain cycles reveals that the doped fibers exhibit high cyclic stability and retain their electrical conductivity. Finally, a directional strain sensing device, which makes use of the linear increase in resistance of the fibers up to 120% strain is demonstrated.

Toughening of a Soft Polar Polythiophene through Copolymerization with Hard Urethane Segments.

Polar polythiophenes with oligoethylene glycol side chains are exceedingly soft materials. A low glass transition temperature and low degree of crystallinity prevents their use as a bulk material. The synthesis of a copolymer comprising 1) soft polythiophene blocks with tetraethylene glycol side chains, and 2) hard urethane segments is reported. The molecular design is contrary to that of other semiconductor-insulator copolymers, which typically combine a soft nonconjugated spacer with hard conjugated segments. Copolymerization of polar polythiophenes and urethane segments results in a ductile material that can be used as a free-standing solid. The copolymer displays a storage modulus of 25 MPa at room temperature, elongation at break of 95%, and a reduced degree of swelling due to hydrogen bonding. Both chemical doping and electrochemical oxidation reveal that the introduction of urethane segments does not unduly reduce the hole charge-carrier mobility and ability to take up charge. Further, stable operation is observed when the copolymer is used as the active layer of organic electrochemical transistors.

Ground-state electron transfer in all-polymer donor-acceptor heterojunctions.

Doping of organic semiconductors is crucial for the operation of organic (opto)electronic and electrochemical devices. Typically, this is achieved by adding heterogeneous dopant molecules to the polymer bulk, often resulting in poor stability and performance due to dopant sublimation or aggregation. In small-molecule donor-acceptor systems, charge transfer can yield high and stable electrical conductivities, an approach not yet explored in all-conjugated polymer systems. Here, we report ground-state electron transfer in all-polymer donor-acceptor heterojunctions. Combining low-ionization-energy polymers with high-electron-affinity counterparts yields conducting interfaces with resistivity values five to six orders of magnitude lower than the separate single-layer polymers. The large decrease in resistivity originates from two parallel quasi-two-dimensional electron and hole distributions reaching a concentration of ∼1013 cm-2. Furthermore, we transfer the concept to three-dimensional bulk heterojunctions, displaying exceptional thermal stability due to the absence of molecular dopants. Our findings hold promise for electro-active composites of potential use in, for example, thermoelectrics and wearable electronics.

Thermally Activated in Situ Doping Enables Solid-State Processing of Conducting Polymers.

Free-standing bulk structures encompassing highly doped conjugated polymers are currently heavily explored for wearable electronics as thermoelectric elements, conducting fibers, and a plethora of sensory devices. One-step manufacturing of such bulk structures is challenging because the interaction of dopants with conjugated polymers results in poor solution and solid-state processability, whereas doping of thick conjugated polymer structures after processing suffers from diffusion-limited transport of the dopant. Here, we introduce the concept of thermally activated latent dopants for in situ bulk doping of conjugated polymers. Latent dopants allow for noninteractive coprocessing of dopants and polymers, while thermal activation eliminates any thickness-dependent diffusion and activation limitations. Two latent acid dopants were synthesized in the form of thermal acid generators based on aryl sulfonic acids and an o-nitrobenzyl capping moiety. First, we show that these acid dopant precursors can be coprocessed noninteractively with three different polythiophenes. Second, the polymer films were doped in situ through thermal activation of the dopants. Ultimately, we demonstrate that solid-state processing with a latent acid dopant can be readily carried out and that it is possible to dope more than 100 µm-thick polymer films through thermal activation of the latent dopant.

Diffusion-Limited Crystallization: A Rationale for the Thermal Stability of Non-Fullerene Solar Cells.

Organic solar cells are thought to suffer from poor thermal stability of the active layer nanostructure, a common belief that is based on the extensive work that has been carried out on fullerene-based systems. We show that a widely studied non-fullerene acceptor, the indacenodithienothiophene-based acceptor ITIC, crystallizes in a profoundly different way as compared to fullerenes. Although fullerenes are frozen below the glass-transition temperature Tg of the photovoltaic blend, ITIC can undergo a glass-crystal transition considerably below its high Tg of ∼180 °C. Nanoscopic crystallites of a low-temperature polymorph are able to form through a diffusion-limited crystallization process. The resulting fine-grained nanostructure does not evolve further with time and hence is characterized by a high degree of thermal stability. Instead, above Tg, the low temperature polymorph melts, and micrometer-sized crystals of a high-temperature polymorph develop, enabled by more rapid diffusion and hence long-range mass transport. This leads to the same detrimental decrease in photovoltaic performance that is known to occur also in the case of fullerene-based blends. Besides explaining the superior thermal stability of non-fullerene blends at relatively high temperatures, our work introduces a new rationale for the design of bulk heterojunctions that is not based on the selection of high- Tg materials per se but diffusion-limited crystallization. The planar structure of ITIC and potentially other non-fullerene acceptors readily facilitates the desired glass-crystal transition, which constitutes a significant advantage over fullerenes, and may pave the way for truly stable organic solar cells.

Enhanced Thermoelectric Power Factor of Tensile Drawn Poly(3-hexylthiophene).

The thermoelectric power factor of a broad range of organic semiconductors scales with their electrical conductivity according to a widely obeyed power law, and therefore, strategies that permit this empirical trend to be surpassed are highly sought after. Here, tensile drawing of the conjugated polymer poly(3-hexylthiophene) (P3HT) is employed to create free-standing films with a high degree of uniaxial alignment. Along the direction of orientation, sequential doping with a molybdenum tris(dithiolene) complex leads to a 5-fold enhancement of the power factor beyond the predicted value, reaching up to 16 µW m-1 K-2 for a conductivity of about 13 S cm-1. Neither stretching nor doping affect the glass transition temperature of P3HT, giving rise to robust free-standing materials that are of interest for the design of flexible thermoelectric devices.

Double doping of conjugated polymers with monomer molecular dopants.

Molecular doping is a crucial tool for controlling the charge-carrier concentration in organic semiconductors. Each dopant molecule is commonly thought to give rise to only one polaron, leading to a maximum of one donor:acceptor charge-transfer complex and hence an ionization efficiency of 100%. However, this theoretical limit is rarely achieved because of incomplete charge transfer and the presence of unreacted dopant. Here, we establish that common p-dopants can in fact accept two electrons per molecule from conjugated polymers with a low ionization energy. Each dopant molecule participates in two charge-transfer events, leading to the formation of dopant dianions and an ionization efficiency of up to 200%. Furthermore, we show that the resulting integer charge-transfer complex can dissociate with an efficiency of up to 170%. The concept of double doping introduced here may allow the dopant fraction required to optimize charge conduction to be halved.

All-Organic Textile Thermoelectrics with Carbon-Nanotube-Coated n-Type Yarns.

Thermoelectric textiles that are able to generate electricity from heat gradients may find use as power sources for a wide range of miniature wearable electronics. To realize such thermoelectric textiles, both p- and n-type yarns are needed. The realization of air-stable and flexible n-type yarns, i.e., conducting yarns where electrons are the majority charge carriers, presents a considerable challenge due to the scarcity of air-stable n-doped organic materials. Here, we realize such n-type yarns by coating commercial sewing threads with a nanocomposite of multiwalled carbon nanotubes (MWNTs) and poly(N-vinylpyrrolidone) (PVP). Our n-type yarns have a bulk conductivity of 1 S cm-1 and a Seebeck coefficient of -14 µV K-1, which is stable for several months at ambient conditions. We combine our coated n-type yarns with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) dyed silk yarns, constituting the p-type component, to realize a textile thermoelectric module with 38 n/p elements, which are capable of producing an open-circuit voltage of 143 mV when exposed to a temperature gradient of 116 °C and a maximum power output of 7.1 nW at a temperature gradient of 80 °C.

Highly stable doping of a polar polythiophene through co-processing with sulfonic acids and bistriflimide.

Doping of organic semiconductors is currently an intensely studied field, since it is a powerful tool to optimize the performance of various organic electronic devices, ranging from organic solar cells, to thermoelectric modules, and bio-medical sensors. Despite recent advances, there is still a need for the development of highly conducting polymer:dopant systems with excellent long term stability and a high resistance to elevated temperatures. In this work we study the doping of the polar polythiophene derivative p(g42T-T) by various sulfonic acids and bistriflimide via different processing techniques. We demonstrate that simple co-processing of p(g42T-T) with an acid dopant yields conductivities of up to 120 S cm-1, which remain stable for more than six months under ambient conditions. Notably, a high conductivity is only achieved if the doping is carried out in air, which can be explained with a doping process that involves an acid mediated oxidation of the polymer through O2. P(g42T-T) doped with the non-toxic and inexpensive 1,3-propanedisulfonic acid was found to retain its electrical conductivity for at least 20 hours upon annealing at 120 °C, which allowed the bulk processing of the doped polymer into conducting, free-standing and flexible films and renders the di-acid a promising alternative to commonly used redox dopants.

Enhanced Electrical Conductivity of Molecularly p-Doped Poly(3-hexylthiophene) through Understanding the Correlation with Solid-State Order.

Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure-property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm-1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10-4 mol cm-3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10-1 cm2 V-1 s-1. Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure-property relationships of strongly doped conjugated polymers.

Polar Side Chains Enhance Processability, Electrical Conductivity, and Thermal Stability of a Molecularly p-Doped Polythiophene.

Molecular doping of organic semiconductors is critical for optimizing a range of optoelectronic devices such as field-effect transistors, solar cells, and thermoelectric generators. However, many dopant:polymer pairs suffer from poor solubility in common organic solvents, which leads to a suboptimal solid-state nanostructure and hence low electrical conductivity. A further drawback is the poor thermal stability through sublimation of the dopant. The use of oligo ethylene glycol side chains is demonstrated to significantly improve the processability of the conjugated polymer p(g4 2T-T)-a polythiophene-in polar aprotic solvents, which facilitates coprocessing of dopant:polymer pairs from the same solution at room temperature. The use of common molecular dopants such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is explored. Doping of p(g4 2T-T) with F4TCNQ results in an electrical conductivity of up to 100 S cm-1 . Moreover, the increased compatibility of the polar dopant F4TCNQ with the oligo ethylene glycol functionalized polythiophene results in a high degree of thermal stability at up to 150 °C.