Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries.

Nanoparticle silicon-graphite composite electrodes are a viable way to advance the cycle life and energy density of lithium-ion batteries. However, characterization of composite electrode architectures is complicated by the heterogeneous mixture of electrode components and nanoscale diameter of particles, which falls beneath the lateral and depth resolution of most laboratory-based instruments. In this work, we report an original laboratory-based scanning probe microscopy approach to investigate composite electrode microstructures with nanometer-scale resolution via contrast in the electronic properties of electrode components. Applying this technique to silicon-based composite anodes demonstrates that graphite, SiOx nanoparticles, carbon black, and LiPAA binder are all readily distinguished by their intrinsic electronic properties, with measured electronic resistivity closely matching their known material properties. Resolution is demonstrated by identification of individual nanoparticles as small as ∼20 nm. This technique presents future utility in multiscale characterization to better understand particle dispersion, localized lithiation, and degradation processes in composite electrodes for lithium-ion batteries.

Microscopy Visualization of Carrier Transport in CdSeTe/CdTe Solar Cells.

Solar cells are essentially minority carrier devices, and it is therefore of central importance to understand the pertinent carrier transport processes. Here, we advanced a transport imaging technique to directly visualize the charge motion and collection in the direction of relevant carrier transport and to understand the cell operation and degradation in state-of-the-art cadmium telluride solar cells. We revealed complex carrier transport profiles in the inhomogeneous polycrystalline thin-film solar cell, with the influence of electric junction, interface, recombination, and material composition. The pristine cell showed a unique dual peak in the carrier transport light intensity decay profile, and the dual peak feature disappeared on a degraded cell after light and heat stressing in the lab. The experiments, together with device modeling, suggested that selenium diffusion plays an important role in carrier transport. The work opens a new forum by which to understand the carrier transport and bridge the gap between atomic/nanometer-scale chemical/structural and submicrometer optoelectronic knowledge.

Double-hole-mediated coupling of dopants and its impact on band gap engineering in TiO2.

A double-hole-mediated coupling of dopants is unraveled and confirmed in TiO2 by density-functional theory calculations. We find that when a dopant complex on neighboring oxygen sites in TiO2 has net two holes, the holes will strongly couple to each other through significant lattice relaxation. The coupling results in the formation of fully filled impurity bands lying above the valence band of TiO2, leading to a much more effective band gap reduction than that induced by monodoping or conventional donor-acceptor codoping. Our results suggest a new path for semiconductor band gap engineering.

Emission Control from Transition Metal Dichalcogenide Monolayers by Aggregation-Induced Molecular Rotors.

Organic-inorganic (O-I) heterostructures, consisting of atomically thin inorganic semiconductors and organic molecules, present synergistic and enhanced optoelectronic properties with a high tunability. Here, we develop a class of air-stable vertical O-I heterostructures comprising a monolayer of transition-metal dichalcogenides (TMDs), including WS2, WSe2, and MoSe2, on top of tetraphenylethylene (TPE) core-based aggregation-induced emission (AIE) molecular rotors. The created O-I heterostructures yields a photoluminescence (PL) enhancement of up to ∼950%, ∼500%, and ∼330% in the top monolayer WS2, MoSe2, and WSe2 as compared to PL in their pristine monolayers, respectively. The strong PL enhancement is mainly attributed to the efficient photogenerated carrier process in the AIE luminogens (courtesy of their restricted intermolecular motions in the solid state) and the charge-transfer process in the created type I O-I heterostructures. Moreover, we observe an improvement in photovoltaic properties of the TMDs in the heterostructures including the quasi-Fermi level splitting, minority carrier lifetime, and light absorption. This work presents an inspiring example of combining stable, highly luminescent AIE-based molecules, with rich photochemistry and versatile applications, with atomically thin inorganic semiconductors for multifunctional and efficient optoelectronic devices.

Protection of GaInP2 Photocathodes by Direct Photoelectrodeposition of MoSx Thin Films.

Catalytic MoSx thin films have been directly photoelectrodeposited on GaInP2 photocathodes for stable photoelectrochemical hydrogen generation. Specifically, the MoSx deposition conditions were controlled to obtain 8-10 nm films directly on p-GaInP2 substrates without ancillary protective layers. The films were nominally composed of MoS2, with additional MoOxSy and MoO3 species detected and showed no long-range crystalline order. The as-deposited material showed excellent catalytic activity toward the hydrogen evolution reaction relative to bare p-GaInP2. Notably, no appreciable photocurrent reduction was incurred by the addition of the photoelectrodeposited MoSx catalyst to the GaInP2 photocathode under light-limited operating conditions, highlighting the advantageous optical properties of the film. The MoSx catalyst also imparted enhanced durability toward photoelectrochemical hydrogen evolution in acidic conditions, maintaining nearly 85% of the initial photocurrent after 50 h of electrolysis. In total, this work demonstrates a simple method for producing dual-function catalyst/protective layers directly on high-performance, planar III-V photoelectrodes for photoelectrochemical energy conversion.

High-Throughput Experimental Study of Wurtzite Mn1-x Zn x O Alloys for Water Splitting Applications.

We used high-throughput experimental screening methods to unveil the physical and chemical properties of Mn1-x Zn x O wurtzite alloys and identify their appropriate composition for effective water splitting application. The Mn1-x Zn x O thin films were synthesized using combinatorial pulsed laser deposition, permitting for characterization of a wide range of compositions with x varying from 0 to 1. The solubility limit of ZnO in MnO was determined using the disappearing phase method from X-ray diffraction and X-ray fluorescence data and found to increase with decreasing substrate temperature due to kinetic limitations of the thin-film growth at relatively low temperature. Optical measurements indicate the strong reduction of the optical band gap down to 2.1 eV at x = 0.5 associated with the rock salt-to-wurtzite structural transition in Mn1-x Zn x O alloys. Transmission electron microscopy results show evidence of a homogeneous wurtzite alloy system for a broad range of Mn1-x Zn x O compositions above x = 0.4. The wurtzite Mn1-x ZnxO samples with the 0.4 < x < 0.6 range were studied as anodes for photoelectrochemical water splitting, with a maximum current density of 340 µA cm-2 for 673 nm-thick films. These Mn1-x Zn x O films were stable in pH = 10, showing no evidence of photocorrosion or degradation after 24 h under water oxidation conditions. Doping Mn1-x Zn x O materials with Ga dramatically increases the electrical conductivity of Mn1-x Zn x O up to ∼1.9 S/cm for x = 0.48, but these doped samples are not active in water splitting. Mott-Schottky and UPS/XPS measurements show that the presence of dopant atoms reduces the space charge region and increases the number of mid-gap surface states. Overall, this study demonstrates that Mn1-x Zn x O alloys hold promise for photoelectrochemical water splitting, which could be enhanced with further tailoring of their electronic properties.

Carrier lifetimes of >1 µs in Sn-Pb perovskites enable efficient all-perovskite tandem solar cells.

All-perovskite-based polycrystalline thin-film tandem solar cells have the potential to deliver efficiencies of >30%. However, the performance of all-perovskite-based tandem devices has been limited by the lack of high-efficiency, low-band gap tin-lead (Sn-Pb) mixed-perovskite solar cells (PSCs). We found that the addition of guanidinium thiocyanate (GuaSCN) resulted in marked improvements in the structural and optoelectronic properties of Sn-Pb mixed, low-band gap (~1.25 electron volt) perovskite films. The films have defect densities that are lower by a factor of 10, leading to carrier lifetimes of greater than 1 microsecond and diffusion lengths of 2.5 micrometers. These improved properties enable our demonstration of >20% efficient low-band gap PSCs. When combined with wider-band gap PSCs, we achieve 25% efficient four-terminal and 23.1% efficient two-terminal all-perovskite-based polycrystalline thin-film tandem solar cells.

Junction Quality of SnO2-Based Perovskite Solar Cells Investigated by Nanometer-Scale Electrical Potential Profiling.

Electron-selective layers (ESLs) and hole-selective layers (HSLs) are critical in high-efficiency organic-inorganic lead halide perovskite (PS) solar cells for charge-carrier transport, separation, and collection. We developed a procedure to assess the quality of the ESL/PS junction by measuring potential distribution on the cross section of SnO2-based PS solar cells using Kelvin probe force microscopy. Using the potential profiling, we compared three types of cells made of different ESLs but otherwise having an identical device structure: (1) cells with PS deposited directly on bare fluorine-doped SnO2 (FTO)-coated glass; (2) cells with an intrinsic SnO2 thin layer on the top of FTO as an effective ESL; and (3) cells with the SnO2 ESL and adding a self-assembled monolayer (SAM) of fullerene. The results reveal two major potential drops or electric fields at the ESL/PS and PS/HSL interfaces. The electric-field ratio between the ESL/PS and PS/HSL interfaces increased in devices as follows: FTO < SnO2-ESL < SnO2 + SAM; this sequence explains the improvements of the fill factor (FF) and open-circuit voltage (Voc). The improvement of the FF from the FTO to SnO2-ESL cells may result from the reduction in voltage loss at the PS/HSL back interface and the improvement of Voc from the prevention of hole recombination at the ESL/PS front interface. The further improvements with adding an SAM is caused by the defect passivation at the ESL/PS interface, and hence, improvement of the junction quality. These nanoelectrical findings suggest possibilities for improving the device performance by further optimizing the SnO2-based ESL material quality and the ESL/PS interface.

Carrier separation and transport in perovskite solar cells studied by nanometre-scale profiling of electrical potential.

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 delocalized nature of holes in (Ga, N) cluster-doped ZnO.

A spin-polarized density-functional theory study is presented here, revealing that a single hole state created by (Ga, N) cluster doping in ZnO contains the contributions from all of the N atoms in the cluster. This is in contrast to the situation where N atoms alone are doped into ZnO, and have a highly localized hole state centered around the dopant N atoms. Hence, this study shows that an enhanced delocalized hole state can be obtained if an appropriate electronic environment is provided.

Imaging of resonant quenching of surface plasmons by quantum dots.

In scanning tunneling microscopy (STM), confinement of surface plasmons to the optical cavity formed at the metallic tunneling gap stimulates the emission of light. We demonstrate that quantum dots (QDs) found in such a cavity give rise to discrete, observable transitions in the tunneling luminescence spectrum due to the resonant extinction of the plasmon. The observed resonances represent a fingerprint of the QD and occur at the optical band gap owing to the nearly simultaneous transfer of carriers from both sides of the tunneling gap to the QD. The resonant quenching of surface plasmons enables a new imaging technique, dubbed plasmon resonance imaging, with a spatial resolution potentially similar to that of STM and the energy resolution of optical spectroscopies. This detection and imaging strategy is not restricted to QDs, being of great interest to an entire spectrum of nanostructures, from molecular assemblies and biomolecules to carbon nanotubes.