Understanding asymmetric switching times in accumulation mode organic electrochemical transistors.

Understanding the factors underpinning device switching times is crucial for the implementation of organic electrochemical transistors in neuromorphic computing, bioelectronics and real-time sensing applications. Existing models of device operation cannot explain the experimental observations that turn-off times are generally much faster than turn-on times in accumulation mode organic electrochemical transistors. Here, using operando optical microscopy, we image the local doping level of the transistor channel and show that turn-on occurs in two stages-propagation of a doping front, followed by uniform doping-while turn-off occurs in one stage. We attribute the faster turn-off to a combination of engineering as well as physical and chemical factors including channel geometry, differences in doping and dedoping kinetics and the phenomena of carrier-density-dependent mobility. We show that ion transport limits the operation speed in our devices. Our study provides insights into the kinetics of organic electrochemical transistors and guidelines for engineering faster organic electrochemical transistors.

Polaron absorption in aligned conjugated polymer films: breakdown of adiabatic treatments and going beyond the conventional mid-gap state model.

This study provides the first experimental polarized intermolecular and intramolecular optical absorption components of field-induced polarons in regioregular poly(3-hexylthiophene-2,5-diyl), rr-P3HT, a polymer semiconductor. Highly aligned rr-P3HT thin films were prepared by a high temperature shear-alignment process that orients polymer backbones along the shearing direction. rr-P3HT in-plane molecular orientation was measured by electron diffraction, and out-of-plane orientation was measured through series of synchrotron X-ray scattering techniques. Then, with molecular orientation quantified, polarized charge modulation spectroscopy was used to probe mid-IR polaron absorption in the ℏω = 0.075 - 0.75 eV range and unambiguously assign intermolecular and intramolecular optical absorption components of hole polarons in rr-P3HT. This data represents the first experimental quantification of these polarized components and allowed long-standing theoretical predictions to be compared to experimental results. The experimental data is discrepant with predictions of polaron absorption based on an adiabatic framework that works under the Born-Oppenheimer approximation, but the data is entirely consistent with a more recent nonadiabatic treatment of absorption based on a modified Holstein Hamiltonian. This nonadiabatic treatment was used to show that both intermolecular and intramolecular polaron coherence break down at length scales significantly smaller than estimated structural coherence in either direction. This strongly suggests that polaron delocalization is fundamentally limited by energetic disorder in rr-P3HT.

The unexpected fast polymerization during the synthesis of a glycolated polythiophene.

Conjugated polymers with ethylene glycol side chains are emerging as ideal materials for bioelectronics, particularly for application in organic electrochemical transistors (OECTs). To improve the OECT device performance, it is important to develop an efficient synthetic strategy that will provide access to novel high-performing materials besides focusing on molecular design. While a lot of efforts are being devoted to designing of new polymers by modifying the glycol side chains, understanding how their nature affects the polymerization kinetics and eventually the polymer structure and properties is not known. In this work, we have studied the influence of the content of the ethylene glycol side chain and its linkage on the formation of the active Grignard monomer species upon Grignard metathesis in three thiophene derivatives. A strong dependence of the monomer's concentration on polymerization was noted in our study indicating that for synthesizing P3MEEMT, a high-performing OECT material, by Kumada catalyst transfer polymerization (KCTP) a minimum of 0.15 M monomer is needed. Furthermore, kinetic studies by GPC show uncontrolled polymerization behavior contrary to the controlled chain growth characteristics of the KCTP.

Microparticles in marine mussels at regional and localized scales across the Salish Sea, Washington.

Microparticles (MP; particles <5 mm) are ubiquitous in marine environments. Understanding MP concentrations at different spatial scales in the Salish Sea, Washington, USA, can provide insight into how ecologically and economically important species may be affected. We collected mussels across the Salish Sea at regional and localized scales, chemically processed tissue to assess MP contamination, and used visual and chemical analyses for particle identification. Throughout the Salish Sea, mussel MP concentrations averaged 0.75 ± 0.09 MP g-1 wet tissue. At a regional scale, we identified slight differences in concentrations and morphotypes of MP while at a localized scale these metrics were not significant and did not differ from controls. In a subset of particles, 20 % were identified as synthetic materials, which include polyethylene terephthalate (PET), polypropylene (PP), polystyrene (PS), and nylon. Differences in MP sources, heterogeneous transport of MP, and distinct shellfish feeding mechanisms may contribute to plastic contamination patterns in the Salish Sea.

Exploiting weak supervision to facilitate segmentation, classification, and analysis of microplastics (<100 µm) using Raman microspectroscopy images.

Reliable quantification and characterization of microplastics are necessary for large-scale and long-term monitoring of their behaviors and evolution in the environment. This is especially true in recent times because of the increase in the production and use of plastics during the pandemic. However, because of the myriad of microplastic morphologies, dynamic environmental forces, and time-consuming and expensive methods to characterize microplastics, it is challenging to understand microplastic transport in the environment. This paper describes a novel approach that compares unsupervised, weakly-supervised, and supervised approaches to facilitate segmentation, classification, and the analysis of <100 µm-sized microplastics without the use of pixel-wise human-labeled data. The secondary aim of this work is to provide insight into what can be accomplished when no human annotations are available, using the segmentation and classification tasks as use cases. In particular, the weakly-supervised segmentation performance surpasses the baseline performance set by the unsupervised approach. Consequently, feature extraction (derived from the segmentation results) provides objective parameters describing microplastic morphologies that will result in better standardization and comparisons of microplastic morphology across future studies. The weakly-supervised performance for microplastic morphology classification (e.g., fiber, spheroid, shard/fragment, irregular) also exceeds the performance of the supervised analogue. Moreover, in contrast to the supervised method, our weakly-supervised approach provides the benefit of pixel-wise detection of microplastic morphology. Pixel-wise detection is used further to improve shape classifications. We also demonstrate a proof-of-concept for distinguishing microplastic particles from non-microplastic particles using verification data from Raman microspectroscopy. As the automation of microplastic monitoring progresses, robust and scalable identification of microplastics based on their morphology may be achievable.

Cross-Dehydrogenative Coupling Polymerization via C-H Activation for the Synthesis of Conjugated Polymers.

Owing to their versatile (opto)electronic properties, conjugated polymers have found application in several organic electronic devices. Cross-coupling reactions such as Stille, Suzuki, Kumada couplings, and direct arylation reactions have proved to be effective for their synthesis. More atom-efficient oxidative direct arylation polymerization has also been reported for making homopolymers. However, growing interest toward donor-acceptor polymers has led to the recent emergence of cross-dehydrogenative coupling (CDC) polymerization to synthesize alternating copolymers without any prefunctionalization of monomers. Metal-catalyzed cross-coupling of two simple arenes via double C-H activation, or of an arene with an alkene via oxidative Heck-type reaction have been used so far for CDC polymerization. In this article, we discuss the development of CDC polymerization protocols along with the relevant small molecule CDC reactions for an improved understanding of these reactions.

Influence of Side Chain Interdigitation on Strain and Charge Mobility of Planar Indacenodithiophene Copolymers.

Indacenodithiophene (IDT) copolymers are a class of conjugated polymers that have limited long-range order and high hole mobilities, which makes them promising candidates for use in deformable electronic devices. Key to their high hole mobilities is the coplanar monomer repeat units within the backbone. Poly(indacenodithiophene-benzothiadiazole) (PIDTC16-BT) and poly(indacenodithiophene-thiapyrollodione) (PIDTC16-TPDC1) are two IDT copolymers with planar backbones, but they are brittle at low molecular weight and have unsuitably high elastic moduli. Substitution of the hexadecane (C16) side chains of the IDT monomer with isocane (C20) side chains was performed to generate a new BT-containing IDT copolymer: PIDTC20-BT. Substitution of the methyl (C1) side chain on the TPD monomer for an octyl (C8) and 6-ethylundecane (C13B) afford two new TPD-containing IDT copolymers named PIDTC16-TPDC8 and PIDTC16-TPDC13B, respectively. Both PIDTC16-TPDC8 and PIDTC16-TPDC13B are relatively well deformable, have a low yield strain, and display significantly reduced elastic moduli. These mechanical properties manifest themselves because the lengthened side chains extending from the TPD-monomer inhibit precise intermolecular ordering. In PIDTC16-BT, PIDTC20-BT and PIDTC16-TPDC1 side chain ordering can occur because the side chains are only present on the IDT subunit, but this results in brittle thin films. In contrast, PIDTC16-TPDC8 and PIDTC16-TPDC13B have disordered side chains, which seems to lead to low hole mobilities. These results suggest that disrupting the interdigitation in IDT copolymers through comonomer side chain extension leads to more ductile thin films with lower elastic moduli, but decreased hole mobility because of altered local order in the respective thin films. Our work, thus, highlights the trade-off between molecular packing structure for deformable electronic materials and provides guidance for designing new conjugated polymers for stretchable electronics.

Ligand Decomposition during Nanoparticle Synthesis: Influence of Ligand Structure and Precursor Selection.

Aliphatic amine and carboxylic acid ligands are widely used as organic solvents during the bottom-up synthesis of inorganic nanoparticles (NPs). Although the ligands' ability to alter final NP properties has been widely studied, side reactivity of these ligands is emerging as an important mechanism to consider. In this work, we study the thermal decomposition of common ligands with varying functional groups (amines and carboxylic acids) and bond saturations (from saturated to polyunsaturated). Here, we investigate how these ligand properties influence decomposition in the absence and presence of precursors used in NP synthesis. We show that during the synthesis of inorganic chalcogenide NPs (Cu2ZnSnS4, Cu x S, and SnS x ) with metal acetylacetonate precursors and elemental sulfur, the ligand pyrolyzes, producing alkylated graphitic species. Additionally, there was less to no ligand decomposition observed during the sulfur-free synthesis of ZnO and CuO with metal acetylacetonate precursors. These results will help guide ligand selection for NP syntheses and improve reaction purity, an important factor in many applications.

Direct Patterning of Perovskite Nanocrystals on Nanophotonic Cavities with Electrohydrodynamic Inkjet Printing.

Overcoming the challenges of patterning luminescent materials will unlock additive and more sustainable paths for the manufacturing of next-generation on-chip photonic devices. Electrohydrodynamic (EHD) inkjet printing is a promising method for deterministically placing emitters on these photonic devices. However, the use of this technique to pattern luminescent lead halide perovskite nanocrystals (NCs), notable for their defect tolerance and impressive optical and spin coherence properties, for integration with optoelectronic devices remains unexplored. In this work, we additively deposit nanoscale CsPbBr3 NC features on photonic structures via EHD inkjet printing. We perform transmission electron microscopy of EHD inkjet printed NCs to demonstrate that the NCs' structural integrity is maintained throughout the printing process. Finally, NCs are deposited with sub-micrometer control on an array of parallel silicon nitride nanophotonic cavities and demonstrate cavity-emitter coupling via photoluminescence spectroscopy. These results demonstrate EHD inkjet printing as a scalable, precise method to pattern luminescent nanomaterials for photonic applications.

In Situ Studies of the Swelling by an Electrolyte in Electrochemical Doping of Ethylene Glycol-Substituted Polythiophene.

Organic mixed ionic electronic conductors (OMIECs) have the potential to enable diverse new technologies, ranging from biosensors to flexible energy storage devices and neuromorphic computing platforms. However, a study of these materials in their operating state, which convolves both passive and potential-driven solvent, cation, and anion ingress, is extremely difficult, inhibiting rational material design. In this report, we present a novel approach to the in situ studies of the electrochemical switching of a prototypical OMIEC based on oligoethylene glycol (oEG) substitution of semicrystalline regioregular polythiophene via grazing-incidence X-ray scattering. By studying the crystal lattice both dry and in contact with the electrolyte while maintaining potential control, we can directly observe the evolution of the crystalline domains and their relationship to film performance in an electrochemically gated transistor. Despite the oEG side-chain enabling bulk electrolyte uptake, we find that the crystalline regions are relatively hydrophobic, exhibiting little (less than one water per thiophene) swelling of the undoped polymer, suggesting that the amorphous regions dominate the reported passive swelling behavior. With applied potential, we observe that the π-π separation in the crystals contracts while the lamella spacing increases in a balanced fashion, resulting in a negligible change in the crystal volume. The potential-induced changes in the crystal structure do not clearly correlate to the electrical performance of the film as an organic electrochemical transistor, suggesting that the transistor performance is strongly influenced by the amorphous regions of the film.

Gaining control over conjugated polymer morphology to improve the performance of organic electronics.

Conjugated polymers (CPs) are widely used in various domains of organic electronics. However, the performance of organic electronic devices can be variable due to the lack of precise predictive control over the polymer microstructure. While the chemical structure of CPs is important, CP microstructure also plays an important role in determining the charge-transport, optical and mechanical properties suitable for a target device. Understanding the interplay between CP microstructure and the resulting properties, as well as predicting and targeting specific polymer morphologies, would allow current comprehension of organic electronic device performance to be improved and potentially enable more facile device optimization and fabrication. In this Feature Article, we highlight the importance of investigating CP microstructure, discuss previous developments in the field, and provide an overview of the key aspects of the CP microstructure-property relationship, carried out in our group over recent years.

Circular Discovery in Small Molecule and Conjugated Polymer Synthetic Methodology.

Simple and efficient methods are a key consideration for small molecule and polymer syntheses. Direct arylation polymerization (DArP) is of increasing interest for preparing conjugated polymers as an effective approach compared to conventional cross-coupling polymerizations. As DArP sees broader utilization, advancements are needed to access materials with improved properties and different monomer structures and to improve the scalability of conjugated polymer synthesis. Presented herein are considerations for developing new methods of conjugated polymer synthesis from small molecule transformations, exploring how DArP has successfully used this approach, and presenting how emerging polymerization methodologies are developing similarly. While it is common to adapt small molecule methods to polymerizations, we demonstrate the ways in which information gained from studying polymerizations can inform and inspire greater advancements in small molecule transformations. This circular approach to organic synthetic method development underlines the value of collaboration between small molecule and polymer-based synthetic research groups.

The effect of side chain engineering on conjugated polymers in organic electrochemical transistors for bioelectronic applications.

Bioelectronics focuses on the establishment of the connection between the ion-driven biosystems and readable electronic signals. Organic electrochemical transistors (OECTs) offer a viable solution for this task. Organic mixed ionic/electronic conductors (OMIECs) rest at the heart of OECTs. The balance between the ionic and electronic conductivities of OMIECs is closely connected to the OECT device performance. While modification of the OMIECs' electronic properties is largely related to the development of conjugated scaffolds, properties such as ion permeability, solubility, flexibility, morphology, and sensitivity can be altered by side chain moieties. In this review, we uncover the influence of side chain molecular design on the properties and performance of OECTs. We summarise current understanding of OECT performance and focus specifically on the knowledge of ionic-electronic coupling, shedding light on the significance of side chain development of OMIECs. We show how the versatile synthetic toolbox of side chains can be successfully employed to tune OECT parameters via controlling the material properties. As the field continues to mature, more detailed investigations into the crucial role side chain engineering plays on the resultant OMIEC properties will allow for side chain alternatives to be developed and will ultimately lead to further enhancements within the field of OECT channel materials.

Conjugated Metal-Organic Macrocycles: Synthesis, Characterization, and Electrical Conductivity.

The dimensional reduction of solids into smaller fragments provides a route to achieve new physical properties and gain deeper insight into the extended parent structures. Here, we report the synthesis of CuTOTP-OR (TOTPn- = 2,3,6,7-tetraoxidotriphenylene), a family of copper-based macrocycles that resemble truncated fragments of the conductive two-dimensional (2D) metal-organic framework Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). The planar metal-organic macrocycles self-assemble into ordered nanotubes with internal diameters of ∼2 nm and short interlayer distances of ∼3.20 Å. Strong π-π stacking interactions between macrocycles facilitate out-of-plane charge transport, and pressed pellet conductivities as high as 2(1) × 10-3 S cm-1 are observed. Peripheral alkyl functionalization enhances solution processability and enables the fabrication of thin-film field-effect transistor devices. Ambipolar charge transport is observed, suggesting that similar behavior may be operative in Cu3(HHTP)2. By coupling the attractive features of metal-organic frameworks with greater processability, these macrocycles enable facile device integration and a more nuanced understanding of out-of-plane charge transport in 2D conductive metal-organic frameworks.

An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization.

The Carothers equation is often used to predict the utility of a small molecule reaction in a polymerization. In this study, we present the mechanistic study of Pd/Ag cocatalyzed cross dehydrogenative coupling (CDC) polymerization to synthesize a donor-acceptor (D-A) polymer of 3,3'-dihexyl-2,2'-bithiophene and 2,2',3,3',5,5',6,6'-octafluorobiphenyl, which go counter to the Carothers equation. It is uncovered that the second chain extension cross-coupling proceeds much more efficiently than the first cross-coupling and the homocoupling side reaction (at least 1 order of magnitude faster) leading to unexpectedly low homocoupling defects and high molecular weight polymers. Kinetic analyses show that C-H bond activation is rate-determining in the first cross-coupling but not in the second cross-coupling. Based on DFT calculations, the high cross-coupling rate in the second cross-coupling was ascribed to the strong Pd-thiophene interaction in the Pd-mediated C-H bond activation transition state, which decreases the energy barrier of the Pd-mediated C-H bond activation. These results have implications beyond polymerizations and can be used to ease the synthesis of a wide range of molecules where C-H bond activation may be the limiting factor.

Molecular Design Strategies toward Improvement of Charge Injection and Ionic Conduction in Organic Mixed Ionic-Electronic Conductors for Organic Electrochemical Transistors.

Expanding the toolbox of the biology and electronics mutual conjunction is a primary aim of bioelectronics. The organic electrochemical transistor (OECT) has undeniably become a predominant device for mixed conduction materials, offering impressive transconduction properties alongside a relatively simple device architecture. In this review, we focus on the discussion of recent material developments in the area of mixed conductors for bioelectronic applications by means of thorough structure-property investigation and analysis of current challenges. Fundamental operation principles of the OECT are revisited, and characterization methods are highlighted. Current bioelectronic applications of organic mixed ionic-electronic conductors (OMIECs) are underlined. Challenges in the performance and operational stability of OECT channel materials as well as potential strategies for mitigating them, are discussed. This is further expanded to sketch a synopsis of the history of mixed conduction materials for both p- and n-type channel operation, detailing the synthetic challenges and milestones which have been overcome to frequently produce higher performing OECT devices. The cumulative work of multiple research groups is summarized, and synthetic design strategies are extracted to present a series of design principles that can be utilized to drive figure-of-merit performance values even further for future OMIEC materials.

Organic building blocks at inorganic nanomaterial interfaces.

This tutorial review presents our perspective on designing organic molecules for the functionalization of inorganic nanomaterial surfaces, through the model of an "anchor-functionality" paradigm. This "anchor-functionality" paradigm is a streamlined design strategy developed from a comprehensive range of materials (e.g., lead halide perovskites, II-VI semiconductors, III-V semiconductors, metal oxides, diamonds, carbon dots, silicon, etc.) and applications (e.g., light-emitting diodes, photovoltaics, lasers, photonic cavities, photocatalysis, fluorescence imaging, photo dynamic therapy, drug delivery, etc.). The structure of this organic interface modifier comprises two key components: anchor groups binding to inorganic surfaces and functional groups that optimize their performance in specific applications. To help readers better understand and utilize this approach, the roles of different anchor groups and different functional groups are discussed and explained through their interactions with inorganic materials and external environments.