Search for: All records

Organic mixed ionic–electronic conductors (OMIECs) are a unique class of soft, conjugated polymeric materials. The simultaneous electronic and ionic transport of OMIECs enables a new type of device, namely, organic electrochemical transistors, among other emerging technologies. However, the dynamic nature—where charge transport, doping kinetics, and morphological changes occur concurrently—poses significant challenges in the characterization and understanding of OMIECs. Recent advances in in situ optical techniques, including ultraviolet–visible–near-infrared spectroscopy, Raman spectroscopy, and microscopy imaging, have provided valuable insights into the charge transport mechanisms and ionic doping dynamics spanning from the microscopic to the device scale. In this perspective, based on several archetypal OMIECs, we survey how spectroscopic signatures were used to reveal key physical processes in these materials. Looking forward, we propose that ultrafast spectroscopy and microscopy techniques—such as transient absorption spectroscopy, terahertz time-domain spectroscopy, pump–probe microscopy, and photothermal microscopy—hold great potential for uncovering more fundamental mechanisms of OMIEC operation, including quasiparticle dynamics, intrinsic electrical conductivity, and carrier mobility, which remain under-explored. Integrating optical characterization with electrochemical measurements will enable in operando studies on state-of-the-art devices, with results further refined by parallel advancements in theoretical modeling. Altogether, we envision in operando optical characterization with spatial, spectral, and temporal resolution across multiple scales as a powerful pathway to advance the understanding of OMIEC mechanisms and their structure–property relationships. 

Atomically thin two-dimensional transition-metal dichalcogenides (2D-TMDs) have emerged as semiconductors for next-generation nanoelectronics. As 2D-TMD-based devices typically utilize metals as the contacts, it is crucial to understand the properties of the 2D-TMD/metal interface, including the characteristics of the Schottky barriers formed at the semiconductor-metal junction. Conventional methods for investigating the Schottky barrier height (SBH) at these interfaces predominantly rely on contact-based electrical measurements with complex gating structures. In this study, we introduce an all-optical approach for non-contact measurement of the SBH, utilizing high-quality WS2/Au heterostructures as a model system. Our approach employs a below-bandgap pump to excite hot carriers from the gold into WS2 with varying thicknesses. By monitoring the resultant carrier density changes within the WS2 layers with a broadband probe, we traced the dynamics and magnitude of charge transfer across the interface. A systematic sweep of the pump wavelength enables us to determine the SBH values and unveil an inverse relationship between the SBH and the thickness of the WS2 layers. First-principles calculations reveal the correlation between the probability of injection and the density of states near the conduction band minimum of WS2. The versatile optical methodology for probing TMD/metal interfaces can shed light on the intricate charge transfer characteristics within various 2D heterostructures, facilitating the development of more efficient and scalable nano-electronic and optoelectronic technologies. 

In recent years, optical pump-probe microscopy (PPM) has become a vital technique for spatiotemporally imaging electronic excitations and charge-carrier transport in metals and semiconductors. However, existing methods are limited by mechanical delay lines with a probe time window of only several nanoseconds (ns), or monochromatic pump and probe sources with restricted spectral coverage and temporal resolution, hindering their amenability in studying relatively slow processes. To bridge these gaps, we introduce a dual-hyperspectral PPM setup with a time window spanning from ns to milliseconds and single-ns resolution. Our method features a wide-field probe tunable from 370 nm to 1000 nm and a pump spanning from 330 nm to 16 µm. We apply this PPM technique to study various two-dimensional metal-halide perovskites (2D-MHPs) as representative semiconductors by imaging their transient responses near the exciton resonances under both above-bandgap, electronic pump excitation, and below-bandgap, vibrational pump excitation. The resulting spatially- and temporally-resolved images reveal insights into heat dissipation, film uniformity, distribution of impurity phases, and film-substrate interfaces. In addition, the single-ns temporal resolution enables the imaging of in-plane strain wave propagation in 2D-MHP single crystals. Our method, which offers extensive spectral tunability and significantly improved time resolution, opens new possibilities for the imaging of charge carriers, heat, and transient phase transformation processes, particularly in materials with spatially-varying composition, strain, crystalline structure, and interfaces.