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Transforming an Ionic Conductor into an Electronic Conductor via Crystallization: In Situ Evolution of Transference Numbers and Structure in (La,Sr)(Ga,Fe)O 3–x Perovskite Thin Films
Mixed-conducting perovskites are workhorse electrochemically active materials, but typical high-temperature processing compromises their catalytic activity and chemo-mechanical integrity. Low-temperature pulsed laser deposition of amorphous films plus mild thermal annealing is an emerging route to form homogeneous mixed conductors with exceptional catalytic activity, but little is known about the evolution of the oxide-ion transport and transference numbers during crystallization. Here the coupled evolution of ionic and electronic transport behavior and structure in room-temperature-grown amorphous (La,Sr)(Ga,Fe)O 3-x films as they crystallize is explored. In situ ac-impedance spectroscopy with and without blocking electrodes, simultaneous capturing-synchrotron-grazing-incidence X-ray diffraction, dc polarization, transmission electron microscopy, and molecular dynamics simulations to evaluate isothermal and non-isothermal crystallization effects and the role of grain boundaries on transference numbers is combined. Ionic conductivity increases by ≈2 orders of magnitude during crystallization, with even larger increases in electronic conductivity. Consequently, as crystallinity increases, LSGF transitions from a predominantly ionic conductor to a predominantly electronic conductor. The roles of evolving lattice structural order, microstructure, and defect chemistry are examined. Grain boundaries appear relatively nonblocking electronically but significantly blocking ionically. The results demonstrate that ionic transference numbers can be tailored over a wide range by tuning crystallinity and microstructure without having to change the cation composition.
Broad Applicability of Electrochemical Impedance Spectroscopy to the Measurement of Oxygen Nonstoichiometry in Mixed Ion and Electron Conductors
Oxygen non-stoichiometry is a fundamental feature of mixed ion and electron conductors (MIECs). In this work a general electrochemical method for determining non-stoichiometry in thin film MIECs, via measurement of the chemical capacitance, is demonstrated using ceria and ceria-zirconia (Ce 0.8 Zr 0.2 O 2-δ ) as representative materials. A.C. impedance data are collected from both materials at high temperature (750-900 °C) under reducing conditions with oxygen partial pressure (pO 2 ) in the range 10-13 to 10-20 atm. Additional measurements of ceria-zirconia films are made under relatively oxidizing conditions with pO 2 in the range 0.2 to 10 -4 atm and temperatures of 800-900 °C. Under reducing conditions, the impedance spectra are described by a simple circuit in which a resistor is in series with a resistor and capacitor in parallel, and thickness dependent measurements are used to resolve the capacitance into interfacial and chemical terms. Under more oxidizing conditions, the impedance spectra (of Ce 0.8 Zr 0.2 O 2-δ ) reveal an additional diffusional feature, which enables determination of the ionic resistance of the film in addition to the capacitance, and hence the transport properties. A generalized mathematical formalism is presented for recovering the non-stoichiometry from the chemical capacitance, without recourse to defect chemical models. The ceria non-stoichiometry values are in good agreement with literature values determined by thermogravimetric measurements but display considerably less scatter and are collected on considerably shorter timescales. Here, the thermodynamic analysis of Ce 0.8 Zr 0.2 O 2-δ corroborates earlier findings that introduction of Zr into ceria enhances its reducibility.
Active Tuning of Optical Constants in the Visible–UV: Praseodymium-Doped Ceria—a Model Mixed Ionic–Electronic Conductor
Mixed ionic-electronic conductors offer chemical and electrical means for active tuning of their optical constants, e.g. with variations in oxygen non-stoichiometry in Pr 0.1 Ce 0.9 O 2-δ , enabling implementation of adaptive thin film optical devices. Here, we demonstrate in-situ chemo-tuning of the extinction coefficient in Pr 0.1 Ce 0.9 O 2-δ at elevated temperatures and provide a tuning model that treats the interdependence of mobile oxygen vacancies and small polarons coupled to variations in optically active praseodymium ions. Further, a new means for electro-tuning of the optical constants of mixed ionic-electronic conductors was demonstrated experimentally and modeled for Pr 0.1 Ce 0.9 O 2-δ thin films deposited on grid-like electrode structures. Modeling of non-steady state optical transmittance modulations in the latter allows for estimation of oxygen vacancy mobility that determines the switching speed of the device. Quenched-in values of nr and k to room temperature become nonvolatile, providing a modulation range in the extinction coefficient of Δk ~0.1 (change of ~800%) and in the refractive index of Δn r ~0.1 (relative to initial n r of ~2.35). Key figures of merit including, transmission optical modulation of ~0.04 per 1 mV nm -1 , switching energy per area of 670 pJ μm -2 and switching times of seconds, were demonstrated, with further improvements possible.
New Chemical Dopant and Counterion Mechanism for Organic Electrochemical Transistors and Organic Mixed Ionic–Electronic Conductors
Abstract Organic mixed ionic–electronic conductors (OMIECs) have varied performance requirements across a diverse application space. Chemically doping the OMIEC can be a simple, low‐cost approach for adapting performance metrics. However, complex challenges, such as identifying new dopant materials and elucidating design rules, inhibit its realization. Here, these challenges are approached by introducing a new n‐dopant, tetrabutylammonium hydroxide (TBA‐OH), and identifying a new design consideration underpinning its success. TBA‐OH behaves as both a chemical n‐dopant and morphology additive in donor acceptor co‐polymer naphthodithiophene diimide‐based polymer, which serves as an electron transporting material in organic electrochemical transistors (OECTs). The combined effects enhance OECT transconductance, charge carrier mobility, and volumetric capacitance, representative of the key metrics underpinning all OMIEC applications. Additionally, when the TBA + counterion adopts an “edge‐on” location relative to the polymer backbone, Coulombic interaction between the counterion and polaron is reduced, and polaron delocalization increases. This is the first time such mechanisms are identified in doped‐OECTs and doped‐OMIECs. The work herein therefore takes the first steps toward developing the design guidelines needed to realize chemical doping as a generic strategy for tailoring performance metrics in OECTs and OMIECs.
The hierarchical structure of organic mixed ionic–electronic conductors and its evolution in water
Polymeric organic mixed ionic–electronic conductors underpin several technologies in which their electrochemical properties are desirable. These properties, however, depend on the microstructure that develops in their aqueous operational environment. We investigated the structure of a model organic mixed ionic–electronic conductor across multiple length scales using cryogenic four-dimensional scanning transmission electron microscopy in both its dry and hydrated states. Four-dimensional scanning transmission electron microscopy allows us to identify the prevalent defects in the polymer crystalline regions and to analyse the liquid crystalline nature of the polymer. The orientation maps of the dry and hydrated polymers show that swelling-induced disorder is mostly localized in discrete regions, thereby largely preserving the liquid crystalline order. Therefore, the liquid crystalline mesostructure makes electronic transport robust to electrolyte ingress. Furthermore, this study demonstrates that cryogenic four-dimensional scanning transmission electron microscopy provides multiscale structural insights into complex, hierarchical structures such as polymeric organic mixed ionic–electronic conductors, even in their hydrated operating state.
Synergistic Evolution of Segmental Motion and Cooperative Relaxation within the Amorphous Phase of Organic Mixed Ionic-Electronic Conductors
Organic mixed ionic-electronic conductors (OMIECs) facilitate a variety of electrochemical processes and feature a heterogeneous microstructure composed of both crystalline and amorphous phases. However, structural evolution in amorphous regions during electrochemical doping remains poorly understood, limiting our understanding of mixed conduction mechanisms. Here, in this work, we develop operando chip calorimetry to probe amorphous phase evolution in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) under swelling and electrochemical (de)doping. Our results reveal that amorphous regions providing ionic transport pathways and those within electronic transport channels undergo heterogeneous, yet synergistic, evolution during electrochemical modulation. The cooperative interplay between segmental motion and relaxation maintains ionic conductivity and intergrain electronic transport upon electrowetting and doping, while facilitating efficient ion hopping and adaptable chain conformations during dedoping. Such synergies are more pronounced in loose structures featuring a fibrillar morphology, which exhibit lower glass transition temperatures (T g ) and higher fragility (m). High-throughput robotic screening further establishes a strong correlation between elevated m/T g ratios and enhanced mixed conduction. These findings elucidate the role of the amorphous phase in the synthesis of OMIECs and underscore the potential of operando chip calorimetry in uncovering structure–property relationships in electroactive polymers.
Mechanisms and stability of Li dynamics in amorphous Li-Ti-P-S-based mixed ionic–electronic conductors: A machine learning molecular dynamics study
Mixed ionic–electronic conductors (MIECs) exhibit both high ionic and electronic conductivity to improve the battery performance. In this work, we investigate the mechanism and stability of transport channels in our recently developed MIEC material, amorphous Ti-doped lithium phosphorus sulfide (LPS), using molecular dynamics (MD) simulations with a 99% accurate machine-learning force field (MLFF) trained on ab initio MD data. The achieved MLFF helps efficient large-scale MD simulations on LPS with three Ti concentrations (10%, 20%, and 30%) and six temperatures (25°C to 225°C) to calculate ionic conductivity, activation energy, Li-ion transport mechanism, and configurational entropy. Results show that ionic conductivities and activation energies are consistent with our recent experimental values. Moreover, Li-ion transport occurs via free-volume diffusion facilitated by the formation of disordered Li-S polyhedra. The enhanced stability of transport channels at 10% and 20% Ti doping, compared to 0% and 30%, is observed by analyzing the vibrational and configurational entropy of these disordered Li-S polyhedra. Overall, this study highlights the utility of MLFF-based large-scale MD simulations in explaining the transport mechanism and the stability of Li-ion in Ti-doped LPS electrolyte with significant computational efficiency.
Ion Pair Uptake in Ion Gel Devices Based on Organic Mixed Ionic–Electronic Conductors
Abstract In organic mixed ionic–electronic conductors (OMIECs), it is critical to understand the motion of ions in the electrolyte and OMIEC. Generally, the focus is on the movement of net charge during gating, and the motion of neutral anion–cation pairs is seldom considered. Uptake of mobile ion pairs by the semiconductor before electrochemical gating (passive uptake) can be advantageous as this can improve device speed, and both ions can participate in charge compensation during gating. Here, such passive ion pair uptake in high‐speed solid‐state devices is demonstrated using an ion gel electrolyte. This is compared to a polymerized ionic liquid (PIL) electrolyte to understand how ion pair uptake affects device characteristics. Using X‐ray photoelectron spectroscopy, the passive uptake of ion pairs from the ion gel into the OMIEC is detected, whereas no uptake is observed with a PIL electrolyte. This is corroborated by X‐ray scattering, which reveals morphological changes to the OMIEC from the uptake of ion pairs. With in situ Raman, a reorganization of both anions and cations is then observed during gating. Finally, the speed and retention of OMIEC‐based neuromorphic devices are tuned by controlling the freedom of charge motion in the electrolyte.
Bridging length scales in organic mixed ionic–electronic conductors through internal strain and mesoscale dynamics
Understanding the structural and dynamic properties of disordered systems at the mesoscale is crucial. This is particularly important in organic mixed ionic-electronic conductors (OMIECs), which undergo significant and complex structural changes when operated in an electrolyte. Here, in this study, we investigate the mesoscale strain, reversibility and dynamics of a model OMIEC material under external electrochemical potential using operando X-ray photon correlation spectroscopy. Our results reveal that strain and structural hysteresis depend on the sample's cycling history, establishing a comprehensive kinetic sequence bridging the macroscopic and microscopic behaviours of OMIECs. Furthermore, we uncover the equilibrium and non-equilibrium dynamics of charge carriers and material-doping states, highlighting the unexpected coupling between charge carrier dynamics and mesoscale order. These findings advance our understanding of the structure-dynamics-function relationships in OMIECs, opening pathways for designing and engineering materials with improved performance and functionality in non-equilibrium states during device operation. Understanding mesoscale structure and dynamics in organic mixed ionic-electronic conductors is crucial. Mesoscale strain kinetics and structural hysteresis have been studied, and they uncover the coupling between charge carrier dynamics and mesoscale order in organic mixed ionic-electronic conductors.
Time-Resolved Structural Kinetics of an Organic Mixed Ionic–Electronic Conductor
The structure and packing of organic mixed ionic–electronic conductors have an especially significant effect on transport properties. In operating devices, this structure is not fixed but is responsive to changes in electrochemical potential, ion intercalation, and solvent swelling. Toward this end, the steady-state and transient structure of the model organic mixed conductor, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), is characterized using multimodal time-resolved operando techniques. Steady-state operando X-ray scattering reveals a doping-induced lamellar expansion of 1.6 Å followed by 0.4 Å relaxation at high doping levels. Time-resolved operando X-ray scattering reveals asymmetric rates of lamellar structural change during doping and dedoping that do not directly depend on potential or charging transients. Further, time-resolved spectroscopy establishes a link between structural transients and the complex kinetics of electronic charge carrier subpopulations, in particular the polaron–bipolaron equilibrium. These findings provide insight into the factors limiting the response time of organic mixed-conductor-based devices, and present the first real-time observation of the structural changes during doping and dedoping of a conjugated polymer system via X-ray scattering.
Direct quantification of ion composition and mobility in organic mixed ionic-electronic conductors
Ion transport in organic mixed ionic-electronic conductors (OMIECs) is crucial due to its direct impact on device response time and operating mechanisms but is often assessed indirectly or necessitates extra assumptions. Operando x-ray fluorescence (XRF) is a powerful, direct probe for elemental characterization of bulk OMIECs and was used to directly quantify ion composition and mobility in a model OMIEC, poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS), during device operation. The first cycle revealed slow electrowetting and cation-proton exchange. Subsequent cycles showed rapid response with minor cation fluctuation (~5%). Comparison with optical-tracked electrochromic fronts revealed mesoscale structure–dependent proton transport. The calculated effective ion mobility demonstrated thickness-dependent behavior, emphasizing an interfacial ion transport pathway with a higher mobile ion density. The decoupling of interfacial effects on bulk ion mobility and the decoupling of cation and proton migration elucidate ion transport in conventional and emerging OMIEC-based devices and has broader implications for other ionic conductors writ large.
Charge Carrier Induced Structural Ordering And Disordering in Organic Mixed Ionic Electronic Conductors
Operational stability underpins the successful application of organic mixed ionic-electronic conductors (OMIECs) in a wide range of fields, including biosensing, neuromorphic computing, and wearable electronics. Here in this work, both the operation and stability of a p-type OMIEC material of various molecular weights are investigated. Electrochemical transistor measurements reveal that device operation is very stable for at least 300 charging/discharging cycles independent of molecular weight, provided the charge density is kept below the threshold where strong charge–charge interactions become likely. When electrochemically charged to higher charge densities, an increase in device hysteresis and a decrease in conductivity due to a drop in the hole mobility arising from long-range microstructural disruptions are observed. By employing operando X-ray scattering techniques, two regimes of polaron-induced structural changes are found: 1) polaron-induced structural ordering at low carrier densities, and 2) irreversible structural disordering that disrupts charge transport at high carrier densities, where charge–charge interactions are significant. These operando measurements also reveal that the transfer curve hysteresis at high carrier densities is accompanied by an analogous structural hysteresis, providing a microstructural basis for such instabilities. This work provides a mechanistic understanding of the structural dynamics and material instabilities of OMIEC materials during device operation.
Small‐Molecule Mixed Ionic‐Electronic Conductors for Efficient N‐Type Electrochemical Transistors: Structure‐Function Correlations
Abstract The fundamental challenge in electron‐transporting organic mixed ionic‐electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6‐type/U‐shaped non‐fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1 g to 3 g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Y n series: a U‐shaped/planar core, close π–π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion‐electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high transconductance of 16.5 mS, an on/off current ratio of ~10 6 , and a turn‐on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY‐based OECT performance in terms of denser n gY OEG content, increased crystallite dimensions with decreased long‐range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small‐molecule‐based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small‐molecule OMIECs.
Small‐Molecule Mixed Ionic‐Electronic Conductors for Efficient N‐Type Electrochemical Transistors: Structure‐Function Correlations
Abstract The fundamental challenge in electron‐transporting organic mixed ionic‐electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6‐type/U‐shaped non‐fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1 g to 3 g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Y n series: a U‐shaped/planar core, close π–π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion‐electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high transconductance of 16.5 mS, an on/off current ratio of ~10 6 , and a turn‐on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY‐based OECT performance in terms of denser n gY OEG content, increased crystallite dimensions with decreased long‐range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small‐molecule‐based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small‐molecule OMIECs.
Mixed Ionic–Electronic Conductor of Perovskite Li x La y MO 3-δ toward Carbon-Free Cathode for Reversible Lithium–Air Batteries
Mixed ionic–electronic conductors (MIECs) can play a pivotal role in achieving high energies and power densities in rechargeable batteries owing to their ability to simultaneously conduct ions and electrons. In our study, a new strategy is proposed wherein late 3d transition metals (TMs) are substituted into a perovskite Li-ion conductor to transform it into a Li-containing MIEC. First-principles calculations show that perovskite Li x La y MO 3 with late 3d TMs have a low oxygen vacancy formation energy, implying high electron carrier concentrations corresponding to high electronic conductivity. The activation barriers for Li diffusion in Li x La y MO 3 (M = Ti, Cr, Mn, Fe, and Co) are below 0.411 eV, resulting in high Li-ion conductivity. The designed perovskites of Li0.34La 0.55 MnO 3-δ experimentally prove to have high electronic (2.04 × 10 -3 S cm -1 ) and Li-ion (8.53 × 10 -5 S cm -1 ) conductivities, and when applied in a carbon-free cathode of a Li–air cell, they deliver superior reversibility at 0.21 mAh cm -2 over 100 charge/discharge cycles while avoiding the degradation associated with carbonaceous materials. Finally, this strategy enables the effective design of Li-conducting MIEC and reversible Li–air batteries.
Role of aggregates and microstructure of mixed-ionic–electronic-conductors on charge transport in electrochemical transistors
Synthetic efforts have delivered a library of organic mixed ionic–electronic conductors (OMIECs) with high performance in electrochemical transistors. The most promising materials are redox-active conjugated polymers with hydrophilic side chains that reach high transconductances in aqueous electrolytes due to volumetric electrochemical charging. Current approaches to improve transconductance and device stability focus mostly on materials chemistry including backbone and side chain design. However, other parameters such as the initial microstructure and microstructural rearrangements during electrochemical charging are equally important and are influenced by backbone and side chain chemistry. In this study, we employ a polymer system to investigate the fundamental electrochemical charging mechanisms of OMIECs. We couple in situ electronic charge transport measurements and spectroelectrochemistry with ex situ X-ray scattering electrochemical charging experiments and find that polymer chains planarize during electrochemical charging. Our work shows that the most effective conductivity modulation is related to electrochemical accessibility of well-ordered, interconnected aggregates that host high mobility electronic charge carriers. Electrochemical stress cycling induces microstructural changes, but we find that these aggregates can largely maintain order, providing insights on the structural stability and reversibility of electrochemical charging in these systems. Finally, this work shows the importance of material design for creating OMIECs that undergo structural rearrangements to accommodate ions and electronic charge carriers during which percolating networks are formed for efficient electronic charge transport.
AI‐Accelerated Optimization of Self‐Assembled Organic Mixed Ionic‐Electronic Conductors (OMIEC) (Final Report)
This document describes research activities, products and outcomes of a DOE-funded program to help accelerate development of Organic Mixed Ionic Electronic Conductors (OMIECs) using neutron scattering and high-throughput experimentation. OMIECs are organic materials that conduct both ionic and electronic charge carriers. For these new OMIEC materials, self-assembling ion-conducting block copolymers (BCPs) are used as a structural template for electronic conducting polymers. This forms OMIECs with long-range structural order that can help facilitate long-range electronic transport. The conductive properties of OMIECs are closely associated with their structure, which is affected by solution conditions and polymer macromolecular designs. Thus high-throughput experimentation has been implemented to explore this large design space effectively. The BCP-CP OMIEC systems explored are composed of ion-conducting diblock or triblock copolymers containing polyethylene oxide (PEO), di(ethylene glycol) ethyl ether acrylate (DEGEEA) or poly(ethylene glycol) methyl ether acrylate) (PEGMEA) hydrophilic blocks. These blocks will be coupled with either polypropylene oxide (PPO) or polyheptafluorobutyl acrylate (PHFBA) hydrophobic blocks to drive assembly. The electronic conducting component consists of several different types of conjugated polymers. Small angle scattering of neutrons and X-rays (SANS/SAXS) as well as electrochemical analysis have been coupled with modern algorithms for autonomous research using artificial intelligence (AI).