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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. 

Two-dimensional hybrid metal-halide perovskites (2D-MHPs) have emerged as important solution-processed semiconductors with favorable optical and electronic properties for diverse applications in photovoltaics, optoelectronics, and spintronics. The quasi-2D layered structures, featuring large acoustic impedance mismatches between the organic and inorganic sublattices, are expected to result in distinct and anisotropic thermal transport properties along the cross-plane and in-plane directions. Here, we introduce transducer-free vibrational-pump-visible-probe (VPVP) approaches that enable accurate quantification of anisotropic thermal transport properties in various archetypical single-crystalline 2D-MHPs. Specifically, using VPVP spectroscopy and VPVP microscopy, we measure the anisotropic thermal diffusivities of 2D-MHPs with systematically varied Pb-I octahedral layer thicknesses, as well as organic spacer types and lengths, revealing how these structural parameters alter the cross-plane and in-plane thermal transport properties in distinct ways. While diffuse interface scattering plays an important role in dictating cross-plane thermal transport, in-plane thermal transport is primarily determined by phonon transport within interconnected inorganic layers. Density functional theory incorporating four-phonon scatterings provides further insight into the low thermal conductivity and modest thermal conduction anisotropy in 2D-MHPs. Our work demonstrates a new all-optical and noncontact method, which requires minimal sample preparation and allows direct visualization of cross-plane and in-plane thermal transport, potentially compatible with sample environments. The demonstrated VPVP approaches can advance understanding of thermal transport in 2D-MHPs as well as wide-ranging hybrid and polymeric semiconductors beyond 2D-MHPs. 

Third-generation photovoltaic materials, including metal halide perovskites (MHPs), colloidal quantum dots (QDs), copper zinc tin sulfide (CZTS), and organic semiconductors, among others, have become attractive in the past two decades. Unlike their first- and second-generation counterparts, these advanced materials boast properties beyond mere photovoltaic performance, such as mechanical flexibility, light weight, and cost-effectiveness. Meanwhile, these materials possess more intricate crystalline structures that aid in understanding and predicting their transport properties. In particular, the distinctive phonon dispersions in MHPs, the layered architecture in quasi-two-dimensional (2D) perovskites, the strong quantum confinement in QDs, and the complex crystal structures interspersed with abundant disorders in quaternary CZTS result in unique and sometimes anomalous thermal transport behaviors. Concurrently, the criticality of thermal management in applications such as photovoltaics, thermoelectrics, light emitting diodes, and photodetection devices has received increased recognition, considering that many of these third-generation photovoltaic materials are not good thermal conductors. Effective thermal management necessitates precise measurement, advanced modeling, and a profound understanding and interpretation of thermal transport properties in these novel materials. In this review, we provide a comprehensive summary of various techniques for measuring thermal transport properties of these materials and discuss the ultralow thermal conductivities of three-dimensional (3D) MHPs, superlattice-like thermal transport in 2D perovskites, and novel thermal transport characteristics inherent in QDs and CZTS. By collecting and comparing the literature-reported results, we offer a thorough discussion on the thermal transport phenomenon in these materials. The collective understanding from the literature in this area, as reviewed in this article, can provide guidance for improving thermal management across a wide spectrum of applications extending beyond photovoltaics.