We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS2) through covalent chemical functionalization, and thereby directly influence the ...kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS2 functionalized with the most electron donating functional group (p-(CH3CH2)2NPh-MoS2) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS2. The p-(CH3CH2)2NPh-MoS2 is more stable than unfunctionalized metallic MoS2 and outperforms unfunctionalized metallic MoS2 for continuous H2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS2 nanosheet. The functional groups preserve the metallic nature of the MoS2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.
Organometal-halide perovskite solar cells have greatly improved in just a few years to a power conversion efficiency exceeding 20%. This technology shows unprecedented promise for terawatt-scale ...deployment of solar energy because of its low-cost, solution-based processing and earth-abundant materials. We have studied charge separation and transport in perovskite solar cells-which are the fundamental mechanisms of device operation and critical factors for power output-by determining the junction structure across the device using the nanoelectrical characterization technique of Kelvin probe force microscopy. The distribution of electrical potential across both planar and porous devices demonstrates p-n junction structure at the TiO2/perovskite interfaces and minority-carrier diffusion/drift operation of the devices, rather than the operation mechanism of either an excitonic cell or a p-i-n structure. Combining the potential profiling results with solar cell performance parameters measured on optimized and thickened devices, we find that carrier mobility is a main factor that needs to be improved for further gains in efficiency of the perovskite solar cells.
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.
We developed a monolithic CdTe–PbS tandem solar cell architecture in which both the CdTe and PbS absorber layers are solution-processed from nanocrystal inks. Due to their tunable nature, PbS quantum ...dots (QDs), with a controllable band gap between 0.4 and ∼1.6 eV, are a promising candidate for a bottom absorber layer in tandem photovoltaics. In the detailed balance limit, the ideal configuration of a CdTe (E g = 1.5 eV)–PbS tandem structure assumes infinite thickness of the absorber layers and requires the PbS band gap to be 0.75 eV to theoretically achieve a power conversion efficiency (PCE) of 45%. However, modeling shows that by allowing the thickness of the CdTe layer to vary, a tandem with efficiency over 40% is achievable using bottom cell band gaps ranging from 0.68 and 1.16 eV. In a first step toward developing this technology, we explore CdTe–PbS tandem devices by developing a ZnTe–ZnO tunnel junction, which appropriately combines the two subcells in series. We examine the basic characteristics of the solar cells as a function of layer thickness and bottom-cell band gap and demonstrate open-circuit voltages in excess of 1.1 V with matched short circuit current density of 10 mA/cm2 in prototype devices.
Although molecular charge-transfer doping is widely used to manipulate carrier density in organic semiconductors, only a small fraction of charge carriers typically escape the Coulomb potential of ...dopant counterions to contribute to electrical conductivity. Here, we utilize microwave and direct-current (DC) measurements of electrical conductivity to demonstrate that a high percentage of charge carriers in redox-doped semiconducting single-walled carbon nanotube (s-SWCNT) networks is delocalized as a free carrier density in the π-electron system (estimated as >46% at high doping densities). The microwave and four-point probe conductivities of hole-doped s-SWCNT films quantitatively match over almost 4 orders of magnitude in conductance, indicating that both measurements are dominated by the same population of delocalized carriers. We address the relevance of this surprising one-to-one correspondence by discussing the degree to which local environmental parameters (e.g., tube–tube junctions, Coulombic stabilization, and local bonding environment) may impact the relative magnitudes of each transport measurement.
Methylammonium lead iodide (MAPbI
) exhibits exceptional photovoltaic performance, but there remains substantial controversy over the existence and impact of ferroelectricity on the photovoltaic ...response. We confirm ferroelectricity in MAPbI
single crystals and demonstrate mediation of the electronic response by ferroelectric domain engineering. The ferroelectric response sharply declines above 57°C, consistent with the tetragonal-to-cubic phase transition. Concurrent band excitation piezoresponse force microscopy-contact Kelvin probe force microscopy shows that the measured response is not dominated by spurious electrostatic interactions. Large signal poling (>16 V/cm) orients the permanent polarization into large domains, which show stabilization over weeks. X-ray photoemission spectroscopy results indicate a shift of 400 meV in the binding energy of the iodine core level peaks upon poling, which is reflected in the carrier concentration results from scanning microwave impedance microscopy. The ability to control the ferroelectric response provides routes to increase device stability and photovoltaic performance through domain engineering.
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