Nanoscale Photoexcited Carrier Dynamics in Perovskites.

The optoelectronic properties of lead halide perovskite thin films can be tuned through compositional variations and strain, but the associated nanocrystalline structure makes it difficult to untangle the link between composition, processing conditions, and ultimately material properties and degradation. Here, we study the effect of processing conditions and degradation on the local photoconductivity dynamics in [(CsPbI3)0.05(FAPbI3)0.85(MAPbBr3)0.15] and (FA0.7Cs0.3PbI3) perovskite thin films using temporally and spectrally resolved microwave near-field microscopy with a temporal resolution as high as 5 ns and a spatial resolution better than 50 nm. For the latter FACs formulation, we find a clear effect of the process annealing temperature on film morphology, stability, and spatial photoconductivity distribution. After exposure of samples to ambient conditions and illumination, we find spectral evidence of halide segregation-induced degradation below the instrument resolution limit for the mixed halide formulation, while we find a clear spatially inhomogeneous increase in the carrier lifetime for the FACs formulation annealed at 180 °C.

Spatially Resolved Persistent Photoconductivity in MoS2-WS2 Lateral Heterostructures.

The optical and electronic properties of 2D semiconductors are intrinsically linked via the strong interactions between optically excited bound species and free carriers. Here we use near-field scanning microwave microscopy (SMM) to image spatial variations in photoconductivity in MoS2-WS2 lateral multijunction heterostructures using photon energy-resolved narrowband illumination. We find that the onset of photoconductivity in individual domains corresponds to the optical absorption onset, confirming that the tightly bound excitons in transition metal dichalcogenides can nonetheless dissociate into free carriers. These photogenerated carriers are most likely n-type and are seen to persist for up to days. Informed by finite element modeling we reveal that they can increase the carrier density by up to 200 times. This persistent photoconductivity appears to be dominated by contributions from the multilayer MoS2 domains, and we attribute the flake-wide response in part to charge transfer across the heterointerface. Spatial correlation of our SMM imaging with photoluminescence (PL) mapping confirms the strong link between PL peak emission photon energy, PL intensity, and the local accumulated charge. This work reveals the spatially and temporally complex optoelectronic response of these systems and cautions that properties measured during or after illumination may not reflect the true dark state of these materials but rather a metastable charged state.

Electronic and Morphological Inhomogeneities in Pristine and Deteriorated Perovskite Photovoltaic Films.

We perform scanning microwave microscopy (SMM) to study the spatially varying electronic properties and related morphology of pristine and degraded methylammonium lead-halide (MAPI) perovskite films fabricated under different ambient humidity. We find that higher processing humidity leads to the emergence of increased conductivity at the grain boundaries but also correlates with the appearance of resistive grains that contain PbI2. Deteriorated films show larger and increasingly insulating grain boundaries as well as spatially localized regions of reduced conductivity within grains. These results suggest that while humidity during film fabrication primarily benefits device properties due to the passivation of traps at the grain boundaries and self-doping, it also results in the emergence of PbI2-containing grains. We further establish that MAPI film deterioration under ambient conditions proceeds via the spatially localized breakdown of film conductivity, both at grain boundaries and within grains, due to local variations in susceptibility to deterioration. These results confirm that PbI2 has both beneficial and adverse effects on device performance and provide new means for device optimization by revealing spatial variations in sample conductivity as well as morphological differences in resistance to sample deterioration.

Near-Field Control and Imaging of Free Charge Carrier Variations in GaN Nanowires.

Despite their uniform crystallinity, the shape and faceting of semiconducting nanowires (NWs) can give rise to variations in structure and associated electronic properties. Here we develop a hybrid scanning probe-based methodology to investigate local variations in electronic structure across individual n-doped GaN NWs integrated into a transistor device. We perform scanning microwave microscopy (SMM), which we combine with scanning gate microscopy (SGM) to determine the free-carrier SMM signal contribution and image local charge carrier density variations. In particular, we find significant variations in free carriers across NWs, with a higher carrier density at the wire facets. By increasing the local carrier density through tip-gating, we find that the tip injects current into the NW with strongly localized current when positioned over the wire vertices. These results suggest that the strong variations in electronic properties observed within NWs have significant implications for device design and may lead to new paths to optimization.

Microwave near-field imaging of two-dimensional semiconductors.

Optimizing new generations of two-dimensional devices based on van der Waals materials will require techniques capable of measuring variations in electronic properties in situ and with nanometer spatial resolution. We perform scanning microwave microscopy (SMM) imaging of single layers of MoS2 and n- and p-doped WSe2. By controlling the sample charge carrier concentration through the applied tip bias, we are able to reversibly control and optimize the SMM contrast to image variations in electronic structure and the localized effects of surface contaminants. By further performing tip bias-dependent point spectroscopy together with finite element simulations, we distinguish the effects of the quantum capacitance and determine the local dominant charge carrier species and dopant concentration. These results underscore the capability of SMM for the study of 2D materials to image, identify, and study electronic defects.

GaN nanowire coated with atomic layer deposition of tungsten: a probe for near-field scanning microwave microscopy.

GaN nanowires were coated with tungsten by means of atomic layer deposition. These structures were then adapted as probe tips for near-field scanning microwave microscopy. These probes displayed a capacitive resolution of ~0.03 fF, which surpasses that of a commercial Pt tip. Upon imaging of MoS2 sheets with both the Pt and GaN nanowire tips, we found that the nanowire tips were comparatively immune to surface contamination and far more durable than their Pt counterparts.