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.

Hydration of a Side-Chain-Free n-Type Semiconducting Ladder Polymer Driven by Electrochemical Doping.

We study the organic electrochemical transistor (OECT) performance of the ladder polymer poly(benzimidazobenzophenanthroline) (BBL) in an attempt to better understand how an apparently hydrophobic side-chain-free polymer is able to operate as an OECT with favorable redox kinetics in an aqueous environment. We examine two BBLs of different molecular masses from different sources. Regardless of molecular mass, both BBLs show significant film swelling during the initial reduction step. By combining electrochemical quartz crystal microbalance gravimetry, in-operando atomic force microscopy, and both ex-situ and in-operando grazing incidence wide-angle X-ray scattering (GIWAXS), we provide a detailed structural picture of the electrochemical charge injection process in BBL in the absence of any hydrophilic side-chains. Compared with ex-situ measurements, in-operando GIWAXS shows both more swelling upon electrochemical doping than has previously been recognized and less contraction upon dedoping. The data show that BBL films undergo an irreversible hydration driven by the initial electrochemical doping cycle with significant water retention and lamellar expansion that persists across subsequent oxidation/reduction cycles. This swelling creates a hydrophilic environment that facilitates the subsequent fast hydrated ion transport in the absence of the hydrophilic side-chains used in many other polymer systems. Due to its rigid ladder backbone and absence of hydrophilic side-chains, the primary BBL water uptake does not significantly degrade the crystalline order, and the original dehydrated, unswelled state can be recovered after drying. The combination of doping induced hydrophilicity and robust crystalline order leads to efficient ionic transport and good stability.

A Robust Neural Network for Extracting Dynamics from Electrostatic Force Microscopy Data.

Advances in scanning probe microscopy (SPM) methods such as time-resolved electrostatic force microscopy (trEFM) now permit the mapping of fast local dynamic processes with high resolution in both space and time, but such methods can be time-consuming to analyze and calibrate. Here, we design and train a regression neural network (NN) that accelerates and simplifies the extraction of local dynamics from SPM data directly in a cantilever-independent manner, allowing the network to process data taken with different cantilevers. We validate the NN's ability to recover local dynamics with a fidelity equal to or surpassing conventional, more time-consuming, calibrations using both simulated and real microscopy data. We apply this method to extract accurate photoinduced carrier dynamics on n = 1 butylammonium lead iodide, a halide perovskite semiconductor film that is of interest for applications in both solar photovoltaics and quantum light sources. Finally, we use SHapley Additive exPlanations to evaluate the robustness of the trained model, confirm its cantilever-independence, and explore which parts of the trEFM signal are important to the network.

Imaging Graphene Moiré Superlattices via Scanning Kelvin Probe Microscopy.

Moiré superlattices in van der Waals heterostructures are gaining increasing attention because they offer new opportunities to tailor and explore unique electronic phenomena. Using a combination of lateral piezoresponse force microscopy (LPFM) and scanning Kelvin probe microscopy (SKPM), we directly correlate ABAB and ABCA stacked graphene with local surface potential. We find that the surface potential of the ABCA domains is ∼15 mV higher (smaller work function) than that of the ABAB domains. First-principles calculations show that the different work functions between ABCA and ABAB domains arise from the stacking-dependent electronic structure. Moreover, while the moiré superlattice visualized by LPFM can change with time, imaging the surface potential distribution via SKPM appears more stable, enabling the mapping of ABAB and ABCA domains without tip-sample contact-induced effects. Our results provide a new means to visualize and probe local domain stacking in moiré superlattices along with its impact on electronic properties.

Functional Scanning Probe Imaging of Nanostructured Solar Energy Materials.

From hybrid perovskites to semiconducting polymer/fullerene blends for organic photovoltaics, many new materials being explored for energy harvesting and storage exhibit performance characteristics that depend sensitively on their nanoscale morphology. At the same time, rapid advances in the capability and accessibility of scanning probe microscopy methods over the past decade have made it possible to study processing/structure/function relationships ranging from photocurrent collection to photocarrier lifetimes with resolutions on the scale of tens of nanometers or better. Importantly, such scanning probe methods offer the potential to combine measurements of local structure with local function, and they can be implemented to study materials in situ or devices in operando to better understand how materials evolve in time in response to an external stimulus or environmental perturbation. This Account highlights recent advances in the development and application of scanning probe microscopy methods that can help address such questions while filling key gaps between the capabilities of conventional electron microscopy and newer super-resolution optical methods. Focusing on semiconductor materials for solar energy applications, we highlight a range of electrical and optoelectronic scanning probe microscopy methods that exploit the local dynamics of an atomic force microscope tip to probe key properties of the solar cell material or device structure. We discuss how it is possible to extract relevant device properties using noncontact scanning probe methods as well as how these properties guide materials development. Specifically, we discuss intensity-modulated scanning Kelvin probe microscopy (IM-SKPM), time-resolved electrostatic force microscopy (trEFM), frequency-modulated electrostatic force microscopy (FM-EFM), and cantilever ringdown imaging. We explain these developments in the context of classic atomic force microscopy (AFM) methods that exploit the physics of cantilever motion and photocarrier generation to provide robust, nanoscale measurements of materials physics that are correlated with device operation. We predict that the multidimensional data sets made possible by these types of methods will become increasingly important as advances in data science expand capabilities and opportunities for image correlation and discovery.

Quantitative sub-surface and non-contact imaging using scanning microwave microscopy.

The capability of scanning microwave microscopy for calibrated sub-surface and non-contact capacitance imaging of silicon (Si) samples is quantitatively studied at broadband frequencies ranging from 1 to 20 GHz. Calibrated capacitance images of flat Si test samples with varying dopant density (10(15)-10(19) atoms cm(-3)) and covered with dielectric thin films of SiO2 (100-400 nm thickness) are measured to demonstrate the sensitivity of scanning microwave microscopy (SMM) for sub-surface imaging. Using standard SMM imaging conditions the dopant areas could still be sensed under a 400 nm thick oxide layer. Non-contact SMM imaging in lift-mode and constant height mode is quantitatively demonstrated on a 50 nm thick SiO2 test pad. The differences between non-contact and contact mode capacitances are studied with respect to the main parameters influencing the imaging contrast, namely the probe tip diameter and the tip-sample distance. Finite element modelling was used to further analyse the influence of the tip radius and the tip-sample distance on the SMM sensitivity. The understanding of how the two key parameters determine the SMM sensitivity and quantitative capacitances represents an important step towards its routine application for non-contact and sub-surface imaging.

Submicrosecond time resolution atomic force microscopy for probing nanoscale dynamics.

We propose, simulate, and experimentally validate a new mechanical detection method to analyze atomic force microscopy (AFM) cantilever motion that enables noncontact discrimination of transient events with ~100 ns temporal resolution without the need for custom AFM probes, specialized instrumentation, or expensive add-on hardware. As an example application, we use the method to screen thermally annealed poly(3-hexylthiophene):phenyl-C(61)-butyric acid methyl ester photovoltaic devices under realistic testing conditions over a technologically relevant performance window. We show that variations in device efficiency and nanoscale transient charging behavior are correlated, thereby linking local dynamics with device behavior. We anticipate that this method will find application in scanning probe experiments of dynamic local mechanical, electronic, magnetic, and biophysical phenomena.

Kinetic Suppression of Photoinduced Halide Migration in Wide Bandgap Perovskites via Surface Passivation.

In this work, we study the kinetics of photoinduced halide migration in FA0.8Cs0.2Pb(I0.8Br0.2)3 wide (∼1.69 eV) bandgap perovskites and show that halide migration slows down following surface passivation with (3-aminopropyl) trimethoxysilane (APTMS). We use scanning Kelvin probe microscopy (SKPM) to probe the contact potential difference (CPD) shift under illumination and the kinetics of surface potential relaxation in the dark. Our results show that APTMS-passivated perovskites exhibit a smaller CPD shift under illumination and a slower surface potential relaxation in the dark. We compare the evolution of the photoluminescence spectra of APTMS-passivated and unpassivated perovskites under illumination. We find that APTMS-passivated perovskites exhibit more than 5 times slower photoluminescence red-shift, consistent with the slower surface potential relaxation as observed by SKPM. These observations provide evidence for kinetic suppression of photoinduced halide migration in APTMS-passivated samples, likely due to reduced halide vacancy densities, opening avenues to more efficient and stable devices.

Surface Passivation Suppresses Local Ion Motion in Halide Perovskites.

We use scanning probe microscopy to study ion migration in formamidinium (FA)-containing halide perovskite semiconductor Cs0.22FA0.78Pb(I0.85Br0.15)3 in the presence and absence of chemical surface passivation. We measure the evolving contact potential difference (CPD) using scanning Kelvin probe microscopy (SKPM) following voltage poling. We find that ion migration leads to a ∼100 mV shift in the CPD of control films after poling with 3 V for only a few seconds. Moreover, we find that ion migration is heterogeneous, with domain interfaces leading to a larger CPD shift than domain interiors. Application of (3-aminopropyl)trimethoxysilane (APTMS) as a surface passivator further leads to 5-fold reduction in the CPD shift from ∼100 to ∼20 mV. We use hyperspectral microscopy to confirm that APTMS-treated perovskite films undergo less photoinduced halide migration than control films. We interpret these results as due to a reduction in the halide vacancy concentration after APTMS passivation.

Deterministic fabrication of 3D/2D perovskite bilayer stacks for durable and efficient solar cells.

Realizing solution-processed heterostructures is a long-enduring challenge in halide perovskites because of solvent incompatibilities that disrupt the underlying layer. By leveraging the solvent dielectric constant and Gutmann donor number, we could grow phase-pure two-dimensional (2D) halide perovskite stacks of the desired composition, thickness, and bandgap onto 3D perovskites without dissolving the underlying substrate. Characterization reveals a 3D-2D transition region of 20 nanometers mainly determined by the roughness of the bottom 3D layer. Thickness dependence of the 2D perovskite layer reveals the anticipated trends for n-i-p and p-i-n architectures, which is consistent with band alignment and carrier transport limits for 2D perovskites. We measured a photovoltaic efficiency of 24.5%, with exceptional stability of T99 (time required to preserve 99% of initial photovoltaic efficiency) of >2000 hours, implying that the 3D/2D bilayer inherits the intrinsic durability of 2D perovskite without compromising efficiency.

Nanowire Architectures Improve Ion Uptake Kinetics in Conjugated Polymer Electrochemical Transistors.

Organic electrochemical transistors are believed to face an inherent material design tension between optimizing for ion mobility and for electronic mobility. These devices transduce ion uptake into electrical current, thereby requiring high ion mobility for efficient electrochemical doping and rapid turn-on kinetics and high electronic mobility for the maximum transconductance. Here, we explore a facile route to improve operational kinetics and volumetric capacitance in a high-mobility conjugated polymer (poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)], DPP-DTT) by employing a nanowire morphology. For equivalent thicknesses, the DPP-DTT nanowire films exhibit consistently faster kinetics (∼6-10× faster) compared to a neat DPP-DTT film. The nanowire architectures show ∼4× higher volumetric capacitance, increasing from 7.1 to 27.7 F/cm3, consistent with the porous structure better enabling ion uptake throughout the film. The nanowires also exhibit a small but energetically favorable shift in a threshold voltage of ∼17 mV, making the nanostructured system both faster and energetically easier to electrochemically dope compared to neat films. We explain the variation using two atomic force microscopy methods: in situ electrochemical strain microscopy and nanoinfrared imaging via photoinduced force microscopy. These data show that the nanowire film's structure allows greater swelling and ion uptake throughout the active layer, indicating that the nanowire architecture exhibits volumetric operation, whereas the neat film is largely operating via the field effect. We propose that for higher-mobility materials, casting the active layer in a nanowire form may offer faster kinetics, enhanced volumetric capacitance, and possibly lower threshold voltage while maintaining desirable device performance.

Bismuth Doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals.

We study the effects of bismuth doping on the crystal structure and phase transitions in single crystals of the perovskite semiconductor methylammonium lead tribromide, MAPbBr3. By measuring the temperature-dependent specific heat capacity (Cp), we find that as the Bi doping increases, the phase transition assigned to the cubic to tetragonal phase boundary decreases in temperature. Furthermore, after doping we observe one phase transition between 135 and 155 K, in contrast to two transitions observed in the undoped single crystal. These results appear strikingly similar to previously reported effects of mechanical pressure on perovskite crystal structure. Using X-ray diffraction, we show that the lattice constant decreases as Bi is incorporated into the crystal, as predicted by density functional theory. We propose that bismuth substitutional doping on the lead site is dominant, resulting in BiPb+ centers that induce compressive chemical strain that alters the crystalline phase transitions.

Time-Resolved Electrical Scanning Probe Microscopy of Layered Perovskites Reveals Spatial Variations in Photoinduced Ionic and Electronic Carrier Motion.

We study light-induced dynamics in thin films comprising Ruddlesden-Popper phases of the layered 2D perovskite (C4H9NH3)2PbI4. We probe ionic and electronic carrier dynamics using two complementary scanning probe methods, time-resolved G-mode Kelvin probe force microscopy and fast free time-resolved electrostatic force microscopy, as a function of position, time, and illumination. We show that the average surface photovoltage sign is dominated by the band bending at the buried perovskite-substrate interface. However, the film exhibits substantial variations in the spatial and temporal response of the photovoltage. Under illumination, the photovoltage equilibrates over hundreds of microseconds, a time scale associated with ionic motion and trapped electronic carriers. Surprisingly, we observe that the surface photovoltage of the 2D grain centers evolves more rapidly in time than at the grain boundaries. We propose that the slower evolution at grain boundaries is due to a combination of ion migration occurring between PbI4 planes, as well as electronic carriers traversing grain boundary traps, thereby changing the time-dependent band unbending at grain boundaries. These results provide a model for the photoinduced dynamics in 2D perovskites and are a useful basis for interpreting photovoltage dynamics on hybrid 2D/3D structures.

Noncontact Imaging of Ion Dynamics in Polymer Electrolytes with Time-Resolved Electrostatic Force Microscopy.

Ionic-transport processes govern performance in many classic and emerging devices, ranging from battery storage to modern mixed-conduction organic electrochemical transistors (OECT). Here, we study local ion-transport dynamics in polymer films using time-resolved electrostatic force microscopy (trEFM). We establish a correspondence between local and macroscopic measurements using local trEFM and macroscopic electrical impedance spectroscopy (EIS). We use polymer films doped with lithium bis(trifluoromethane)sulfonimide (LiTFSI) as a model system where the polymer backbone has oxanorbornenedicarboximide repeat units with an oligomeric ethylene oxide side chain of length n. Our results show that the local polymer response measured in the time domain with trEFM follows stretched-exponential relaxation kinetics, consistent with the Havriliak-Negami relaxation we measure in the frequency-domain EIS data for macroscopic samples of the same polymers. Furthermore, we show that the trEFM results capture the same trends as the EIS results-changes in ion dynamics with increasing temperature, increasing salt concentration, and increasing volume fraction of ethylene oxide side chains in the polymer matrix evolve with the same trends in both measurement techniques. We conclude from this correlation that trEFM data reflect, at the nanoscale, the same ionic processes probed in conventional EIS at the device level. Finally, as an example application for emerging materials syntheses, we use trEFM and infrared photoinduced force microscopy (PiFM) to image a diblock copolymer electrolyte for next-generation solid-state energy storage applications.

Identifying Nanoscale Structure-Function Relationships Using Multimodal Atomic Force Microscopy, Dimensionality Reduction, and Regression Techniques.

Correlating nanoscale chemical specificity with operational physics is a long-standing goal of functional scanning probe microscopy (SPM). We employ a data analytic approach combining multiple microscopy modes using compositional information in infrared vibrational excitation maps acquired via photoinduced force microscopy (PiFM) with electrical information from conductive atomic force microscopy. We study a model polymer blend comprising insulating poly(methyl methacrylate) (PMMA) and semiconducting poly(3-hexylthiophene) (P3HT). We show that PiFM spectra are different from FTIR spectra but can still be used to identify local composition. We use principal component analysis to extract statistically significant principal components and principal component regression to predict local current and identify local polymer composition. In doing so, we observe evidence of semiconducting P3HT within PMMA aggregates. These methods are generalizable to correlated SPM data and provide a meaningful technique for extracting complex compositional information that is impossible to measure from any one technique.

Perovskite-Polymer Blends Influencing Microstructures, Nonradiative Recombination Pathways, and Photovoltaic Performance of Perovskite Solar Cells.

Solar cells based on organic-inorganic halide perovskites are now leading the photovoltaic technologies because of their high power conversion efficiency. Recently, there have been debates on the microstructure-related defects in metal halide perovskites (grain size, grain boundaries, etc.) and a widespread view is that large grains are a prerequisite to suppress nonradiative recombination and improve photovoltaic performance, although opinions against it also exist. Herein, we employ blends of methylammonium lead iodide perovskites with an insulating polymer (polyvinylpyrrolidone) that offer the possibility to tune the grain size in order to obtain a fundamental understanding of the photoresponse at the microscopic level. We provide, for the first time, spatially resolved details of the microstructures in such blend systems via Raman mapping, light beam-induced current imaging, and conductive atomic force microscopy. Although the polymer blend systems systematically alter the morphology by creating small grains (more grain boundaries), they reduce nonradiative recombination within the film and enhance its spatial homogeneity of radiative recombination. We attribute this to a reduction in the density of bulk trap states, as evidenced by an order of magnitude higher photoluminescence intensity and a significantly higher open-circuit voltage when the polymer is incorporated into the perovskite films. The solar cells employing blend systems also show nearly hysteresis-free power conversion efficiency ∼17.5%, as well as a remarkable shelf-life stability over 100 days.

Fast time-resolved electrostatic force microscopy: Achieving sub-cycle time resolution.

The ability to measure microsecond- and nanosecond-scale local dynamics below the diffraction limit with widely available atomic force microscopy hardware would enable new scientific studies in fields ranging from biology to semiconductor physics. However, commercially available scanning-probe instruments typically offer the ability to measure dynamics only on time scales of milliseconds to seconds. Here, we describe in detail the implementation of fast time-resolved electrostatic force microscopy using an oscillating cantilever as a means to measure fast local dynamics following a perturbation to a sample. We show how the phase of the oscillating cantilever relative to the perturbation event is critical to achieving reliable sub-cycle time resolution. We explore how noise affects the achievable time resolution and present empirical guidelines for reducing noise and optimizing experimental parameters. Specifically, we show that reducing the noise on the cantilever by using photothermal excitation instead of piezoacoustic excitation further improves time resolution. We demonstrate the discrimination of signal rise times with time constants as fast as 10 ns, and simultaneous data acquisition and analysis for dramatically improved image acquisition times.

Antenna-based ultrahigh vacuum microwave frequency scanning tunneling microscopy system.

The instrumental synthesis of high resolution scanning tunneling microscopy (STM) with the ability to measure differential capacitance with atomic scale resolution is highly desirable for fundamental metrology and for the study of novel physical characteristics. Microwave frequency radiation directed at the tip-sample junction in an STM system allows for such high-resolution differential capacitance information. This ability is particularly critical in ultrahigh vacuum environments, where the additional parameter space afforded by including a capacitance measurement would prove powerful. Here we describe the modifications made to a commercial scanning tunneling microscope to allow for broad microwave frequency alternating current scanning tunneling microscopy (ACSTM) in ultrahigh vacuum conditions using a relatively simple loop antenna and microwave difference frequency detection. The advantages of our system are twofold. First, the use of a removable antenna on a commercial STM prevents interference with other UHV processes while providing a simple method to retrofit any commercial UHV-STM with UHV-ACSTM capability. Second, mounting the microwave antenna on a translator allows for specific tuning of the system to replicate experimental conditions between samples, which is particularly critical in sensitive systems like organic thin films or single molecules where small changes in incident power can affect the results. Our innovation therefore provides a valuable approach to give nearly any commercial STM, be it an ambient or UHV system, the capability to measure atomic-scale microwave studies such as differential capacitance or even single molecule microwave response, and it ensures that experimental ACSTM conditions can be held constant between different samples.

Controlling vertical morphology within the active layer of organic photovoltaics using poly(3-hexylthiophene) nanowires and phenyl-C61-butyric acid methyl ester.

In this study, we demonstrate how the vertical morphology of bulk heterojunction solar cells, with an active layer consisting of self-assembled poly(3-hexylthiophene) (P3HT) nanowires and phenyl-C(61)-butyric acid methyl ester (PCBM), can be beneficially influenced. Most device fabrication routes using similar materials employ an annealing step to influence active layer morphology, but this process can create an unfavorable phase migration where P3HT is driven toward the top of the active layer. In contrast, we demonstrate devices that exhibit an increase in relative fullerene concentration at the top of the active layer by introducing the donor phase as a solid nanowire in the active layer solution and altering the pre-spin drying time. X-ray photoelectron spectroscopy and conductive and photoconductive atomic force microscopy provide detailed images of how the surface of the active layer can be influenced; this is done by tracking the concentration and alignment of P3HT and PCBM domains. Using this new procedure, devices are made with power conversion efficiencies surpassing 2%. Additionally, we show that nanowires grown in the presence of the fullerene perform differently than those that are grown and mixed separately; exposure to the nanowire during self-assembly may allow the fullerene to coat nanowire surfaces and influence the photocurrent within the device.