Visualizing and Controlling of Photogenerated Electron-Hole Pair Separation in Monolayer WS2 Nanobubbles under Piezoelectric Field.

The piezoelectric properties of two-dimensional semiconductor nanobubbles present remarkable potential for application in flexible optoelectronic devices, and the piezoelectric field has emerged as an efficacious pathway for both the separation and migration of photogenerated electron-hole pairs, along with inhibition of recombination. However, the comprehension and control of photogenerated carrier dynamics within nanobubbles still remain inadequate. Hence, this study is dedicated to underscore the importance of in situ detection and detailed characterization of photogenerated electron-hole pairs in nanobubbles to enrich understanding and strategic manipulation in two-dimensional semiconductor materials. Utilizing frequency modulation kelvin probe force microscopy (FM-KPFM) and strain gradient distribution techniques, the existence of a piezoelectric field in monolayer WS2 nanobubbles was confirmed. Combining w/o and with illumination FM-KPFM, second-order capacitance gradient technique and in situ nanoscale tip-enhanced photoluminescence characterization techniques, the interrelationships among the piezoelectric effect, interlayer carrier transfer, and the funneling effect for photocarrier dynamics process across various nanobubble sizes were revealed. Notably, for a WS2/graphene bubble height of 15.45 nm, a 0 mV surface potential difference was recorded in the bubble region w/o and with illumination, indicating a mutual offset of piezoelectric effect, interlayer carrier transfer, and the funneling effect. This phenomenon is prevalent in transition metal dichalcogenides materials exhibiting inversion symmetry breaking. The implication of our study is profound for advancing the understanding of the dynamics of photogenerated electron-hole pair in nonuniform strain piezoelectric systems, and offers a reliable framework for the separation and modulation of photogenerated electron-hole pair in flexible optoelectronic devices and photocatalytic applications.

Metal-insulator-semiconductor photoelectrodes for enhanced photoelectrochemical water splitting.

Photoelectrochemical (PEC) water splitting provides a scalable and integrated platform to harness renewable solar energy for green hydrogen production. The practical implementation of PEC systems hinges on addressing three critical challenges: enhancing energy conversion efficiency, ensuring long-term stability, and achieving economic viability. Metal-insulator-semiconductor (MIS) heterojunction photoelectrodes have gained significant attention over the last decade for their ability to efficiently segregate photogenerated carriers and mitigate corrosion-induced semiconductor degradation. This review discusses the structural composition and interfacial intricacies of MIS photoelectrodes tailored for PEC water splitting. The application of MIS heterostructures across various semiconductor light-absorbing layers, including traditional photovoltaic-grade semiconductors, metal oxides, and emerging materials, is presented first. Subsequently, this review elucidates the reaction mechanisms and respective merits of vacuum and non-vacuum deposition techniques in the fabrication of the insulator layers. In the context of the metal layers, this review extends beyond the conventional scope, not only by introducing metal-based cocatalysts, but also by exploring the latest advancements in molecular and single-atom catalysts integrated within MIS photoelectrodes. Furthermore, a systematic summary of carrier transfer mechanisms and interface design principles of MIS photoelectrodes is presented, which are pivotal for optimizing energy band alignment and enhancing solar-to-chemical conversion efficiency within the PEC system. Finally, this review explores innovative derivative configurations of MIS photoelectrodes, including back-illuminated MIS photoelectrodes, inverted MIS photoelectrodes, tandem MIS photoelectrodes, and monolithically integrated wireless MIS photoelectrodes. These novel architectures address the limitations of traditional MIS structures by effectively coupling different functional modules, minimizing optical and ohmic losses, and mitigating recombination losses.

Enhanced Electromechanical Response Due to Inhomogeneous Strain in Monolayer MoS2.

2D transition metal dichalcogenides (TMDs) exhibit exceptional resilience to mechanical deformation. Applied strain can have pronounced effects on properties such as the bandgaps and exciton dynamics of TMDs, via deformation potentials and electromechanical coupling. In this work, we use piezoresponse force microscopy to show that the inhomogeneous strain from nanobubbles produces dramatic, localized enhancements of the electromechanical response of monolayer MoS2. Nanobubbles with diameters under 100 nm consistently produce an increased piezoresponse that follows the features' topography, while larger bubbles exhibit a halo-like profile, with maximum piezoresponse near the periphery. We show that spatial filtering enables these effects to be eliminated in the quantitative determination of effective piezoelectric or flexoelectric coefficients. Numerical strain modeling reveals a correlation between the hydrostatic strain gradient and the effective piezoelectric coefficient in large MoS2 nanobubbles, suggesting a localized variation in electromechanical coupling due to symmetry reduction induced by inhomogeneous strain.

Elucidating Piezoelectricity and Strain in Monolayer MoS2 at the Nanoscale Using Kelvin Probe Force Microscopy.

Strain engineering modifies the optical and electronic properties of atomically thin transition metal dichalcogenides. Highly inhomogeneous strain distributions in two-dimensional materials can be easily realized, enabling control of properties on the nanoscale; however, methods for probing strain on the nanoscale remain challenging. In this work, we characterize inhomogeneously strained monolayer MoS2 via Kelvin probe force microscopy and electrostatic gating, isolating the contributions of strain from other electrostatic effects and enabling the measurement of all components of the two-dimensional strain tensor on length scales less than 100 nm. The combination of these methods is used to calculate the spatial distribution of the electrostatic potential resulting from piezoelectricity, presenting a powerful way to characterize inhomogeneous strain and piezoelectricity that can be extended toward a variety of 2D materials.

Massively Scalable Self-Assembly of Nano and Microparticle Monolayers via Aerosol Assisted Deposition.

An extremely rapid process for self-assembling well-ordered, nano, and microparticle monolayers via a novel aerosolized method is presented. The novel technique can reach monolayer self-assembly rates as high as 268 cm2 min-1 from a single aerosolizing source and methods to reach faster monolayer self-assembly rates are outlined. A new physical mechanism describing the self-assembly process is presented and new insights enabling high-efficiency nanoparticle monolayer self-assembly are developed. In addition, well-ordered monolayer arrays from particles of various sizes, surface functionality, and materials are fabricated. This new technique enables a 93× increase in monolayer self-assembly rates compared to the current state of the art and has the potential to provide an extremely low-cost option for submicron nanomanufacturing.

Wafer-Scale Synthesis of WS2 Films with In Situ Controllable p-Type Doping by Atomic Layer Deposition.

Wafer-scale synthesis of p-type TMD films is critical for its commercialization in next-generation electro/optoelectronics. In this work, wafer-scale intrinsic n-type WS2 films and in situ Nb-doped p-type WS2 films were synthesized through atomic layer deposition (ALD) on 8-inch α-Al2O3/Si wafers, 2-inch sapphire, and 1 cm2 GaN substrate pieces. The Nb doping concentration was precisely controlled by altering cycle number of Nb precursor and activated by postannealing. WS2 n-FETs and Nb-doped p-FETs with different Nb concentrations have been fabricated using CMOS-compatible processes. X-ray photoelectron spectroscopy, Raman spectroscopy, and Hall measurements confirmed the effective substitutional doping with Nb. The on/off ratio and electron mobility of WS2 n-FET are as high as 105 and 6.85 cm2 V-1 s-1, respectively. In WS2 p-FET with 15-cycle Nb doping, the on/off ratio and hole mobility are 10 and 0.016 cm2 V-1 s-1, respectively. The p-n structure based on n- and p- type WS2 films was proved with a 104 rectifying ratio. The realization of controllable in situ Nb-doped WS2 films paved a way for fabricating wafer-scale complementary WS2 FETs.

Growth Mechanisms and Morphology Engineering of Atomic Layer-Deposited WS2.

Transition-metal dichalcogenides (TMDs) have attracted intense research interest for a broad range of device applications. Atomic layer deposition (ALD), a CMOS compatible technique, can enable the preparation of high-quality TMD films on 8 to 12 in. wafers for large-scale circuit integration. However, the ALD growth mechanisms are still not fully understood. In this work, we systematically investigated the growth mechanisms for WS2 and found them to be strongly affected by nucleation density and film thickness. Transmission electron microscope imaging reveals the coexistence and competition of lateral and vertical growth mechanisms at different growth stages, and the critical thicknesses for each mechanism are obtained. The in-plane lateral growth mode dominates when the film thickness remains less than 5.6 nm (8 layers), while the vertical growth mode dominates when the thickness is greater than 20 nm. From the resulting understanding of these growth mechanisms, the conditions for film deposition were optimized and a maximum grain size of 108 nm was achieved. WS2-based field-effect transistors were fabricated with electron mobility and on/off current ratio up to 3.21 cm2 V-1 s-1 and 105, respectively. Particularly, this work proves the capability of synthesis of TMD films in a wafer scale with excellent controllability of thickness and morphology, enabling many potential applications other than transistors, such as nanowire- or nanosheet-based supercapacitors, batteries, sensors, and catalysis.

Scalable, highly stable Si-based metal-insulator-semiconductor photoanodes for water oxidation fabricated using thin-film reactions and electrodeposition.

Metal-insulator-semiconductor (MIS) structures are widely used in Si-based solar water-splitting photoelectrodes to protect the Si layer from corrosion. Typically, there is a tradeoff between efficiency and stability when optimizing insulator thickness. Moreover, lithographic patterning is often required for fabricating MIS photoelectrodes. In this study, we demonstrate improved Si-based MIS photoanodes with thick insulating layers fabricated using thin-film reactions to create localized conduction paths through the insulator and electrodeposition to form metal catalyst islands. These fabrication approaches are low-cost and highly scalable, and yield MIS photoanodes with low onset potential, high saturation current density, and excellent stability. By combining this approach with a p+n-Si buried junction, further improved oxygen evolution reaction (OER) performance is achieved with an onset potential of 0.7 V versus reversible hydrogen electrode (RHE) and saturation current density of 32 mA/cm2 under simulated AM1.5G illumination. Moreover, in stability testing in 1 M KOH aqueous solution, a constant photocurrent density of ~22 mA/cm2 is maintained at 1.3 V versus RHE for 7 days.

Hyperspectral imaging for high-throughput, spatially resolved spectroscopic scatterometry of silicon nanopillar arrays.

Modern high-throughput nanopatterning techniques, such as nanoimprint lithography, make it possible to fabricate arrays of nanostructures (features with dimensions of 10's to 100's of nm) over large area substrates (cm2 to m2 scale) such as Si wafers, glass sheets, and flexible roll-to-roll webs. The ability to make such large-area nanostructure arrays (LNAs) has created an extensive design space, enabling a wide array of applications including optical devices, such as wire-grid polarizers, transparent conductors, color filters, and anti-reflection surfaces, and building blocks for electronic components, such as ultracapacitors, sensors, and memory storage architectures. However, existing metrology methods will have trouble scaling alongside fabrication methods. Scanning electron microscopy (SEM) and atomic force microscopy (AFM), for instance, have micron scale fields of view (FOV) that preclude comprehensive characterization of LNAs, which may be manufactured at m2 per minute rates. Scatterometry approaches have larger FOVs (typically 100's of µm to a few mm), but traditional scatterometry systems measure samples one point at a time, which also makes them too slow for large-scale LNA manufacturing. In this work, we demonstrate parallelization of the traditional spectroscopic scatterometry approach using hyperspectral imaging, increasing the throughput of the technique by a factor of 106-107. We demonstrate this approach by using hyperspectral imaging and inverse modeling of reflectance spectra to derive 3-dimensional geometric data for Si nanopillar array structures over both mm and cm-scale with µm-scale spatial resolution. This work suggests that geometric measurements for a variety of LNAs can be performed with the potential for high speed over large areas which may be critical for future LNA manufacturing.

Zeta Potential Dependent Self-Assembly for Very Large Area Nanosphere Lithography.

Nanosphere lithography offers a rapid, low-cost approach for patterning of large-area two-dimensional periodic nanostructures. However, a complete understanding of the nanosphere self-assembly process is necessary to enable further development and scaling of this technology. The self-assembly of nanospheres into two-dimensional periodic arrays has previously been attributed solely to the Marangoni force; however, we demonstrate that the ζ potential of the nanosphere solution is critically important for successful self-assembly to occur. We discuss and demonstrate how this insight can be used to greatly increase self-assembled 2D periodic array areas while decreasing patterning time and cost. As a representative application, we fabricate antireflection nanostructures on a transparent flexible polymer substrate suitable for use as a large-area (270 cm2), broadband, omnidirectional antireflection film.

Electrodeposition of crystalline silicon films from silicon dioxide for low-cost photovoltaic applications.

Crystalline-silicon solar cells have dominated the photovoltaics market for the past several decades. One of the long standing challenges is the large contribution of silicon wafer cost to the overall module cost. Here, we demonstrate a simple process for making high-purity solar-grade silicon films directly from silicon dioxide via a one-step electrodeposition process in molten salt for possible photovoltaic applications. High-purity silicon films can be deposited with tunable film thickness and doping type by varying the electrodeposition conditions. These electrodeposited silicon films show about 40 to 50% of photocurrent density of a commercial silicon wafer by photoelectrochemical measurements and the highest power conversion efficiency is 3.1% as a solar cell. Compared to the conventional manufacturing process for solar grade silicon wafer production, this approach greatly reduces the capital cost and energy consumption, providing a promising strategy for low-cost silicon solar cells production.

Structural coloration with hourglass-shaped vertical silicon nanopillar arrays.

We demonstrate that arrays of hourglass-shaped nanopillars patterned into crystalline silicon substrates exhibit vibrant, highly controllable reflective structural coloration. Unlike structures with uniform sidewall profiles, the hourglass profile defines two separate regions on the pillar: a head and a body. The head acts as a suspended Mie resonator and is responsible for resonant reflectance, while the body acts to suppress broadband reflections from the surface. The combination of these effects gives rise to vibrant colors. The size of the nanopillars can be tuned to provide a variety of additive colors, including the RGB primaries. Experimental results are shown for nanopillar arrays fabricated using nanoimprint lithography and plasma etching. A finite difference time domain (FDTD) model is validated against these results and is used to elucidate the electromagnetic response of the nanopillars. Furthermore, a COMSOL model is used to investigate the angle dependence of the reflectance. In view of display applications, a genetic algorithm is used to optimize the nanopillar geometries for RGB color reflective pixels, showing that nearly all of the sRGB color space and most of the Adobe RGB color space can be covered with this technique.

Influence of the Substrate to the LSP Coupling Wavelength and Strength.

Three kinds of typical structures, hemi-/spherical nanoparticles/nanoparticle dimers on the substrate and spherical nanoparticles/nanoparticle dimers half-buried into the substrate, are used for FDTD simulation to theoretically discuss the influence of the substrate to the localized surface plasmon (LSP) coupling when the metal nanoparticles/nanoparticle dimers are locating near a substrate. Simulated results show that the dependencies between the LSP coupling wavelength and the refractive index of the substrate for different structures are not the same, which can be attributed to the different polarization field distributions of LSPs. When light is incident from different directions, the LSP coupling strength are not the same as well and the ratios of the scattering peak intensities depend on the position of the metal nanoparticles or nanoparticle dimers. These phenomenon can be explained by the difference of the local driving electric field intensities which is modulated by the interface between the air and the substrate.

High-Performance Photodetectors Based on Solution-Processed Epitaxial Grown Hybrid Halide Perovskites.

Hybrid organic-inorganic halide perovskites (HOIPs) have recently attracted tremendous attention because of their excellent semiconducting and optoelectronic properties, which exist despite their morphology and crystallinity being far inferior to those of more mature semiconductors, such as silicon and III-V compound semiconductors. Heteroepitaxy can provide a route to achieving high-performance HOIP devices when high crystalline quality and smooth morphology are required, but work on heteroepitaxial HOIPs has not previously been reported. Here, we demonstrate epitaxial growth of methylammonium lead iodide (MAPbI3) on single crystal KCl substrates with smooth morphology and the highest carrier recombination lifetime (∼213 ns) yet reported for nonsingle crystalline MAPbI3. Experimental Raman spectra agree well with theoretical calculations, presenting in particular a sharp peak at 290 cm-1 for the torsional mode of the organic cations, a marker of orientational order and typically lacking in previous reports. Photodetectors were fabricated showing excellent performance, confirming the high quality of the epitaxial MAPbI3 thin films. This work provides a new strategy to enhance the performance of all HOIPs-based devices.

Electrochemical Formation of a p-n Junction on Thin Film Silicon Deposited in Molten Salt.

Herein we report the demonstration of electrochemical deposition of silicon p-n junctions all in molten salt. The results show that a dense robust silicon thin film with embedded junction formation can be produced directly from inexpensive silicates/silicon oxide precursors by a two-step electrodeposition process. The fabricated silicon p-n junction exhibits clear diode rectification behavior and photovoltaic effects, indicating promise for application in low-cost silicon thin film solar cells.

Toward Cost-Effective Manufacturing of Silicon Solar Cells: Electrodeposition of High-Quality Si Films in a CaCl2 -based Molten Salt.

Electrodeposition of Si films from a Si-containing electrolyte is a cost-effective approach for the manufacturing of solar cells. Proposals relying on fluoride-based molten salts have suffered from low product quality due to difficulties in impurity control. Here we demonstrate the successful electrodeposition of high-quality Si films from a CaCl2 -based molten salt. Soluble SiIV -O anions generated from solid SiO2 are electrodeposited onto a graphite substrate to form a dense film of crystalline Si. Impurities in the deposited Si film are controlled at low concentrations (both B and P are less than 1 ppm). In the photoelectrochemical measurements, the film shows p-type semiconductor character and large photocurrent. A p-n junction fabricated from the deposited Si film exhibits clear photovoltaic effects. This study represents the first step to the ultimate goal of developing a cost-effective manufacturing process for Si solar cells based on electrodeposition.

Out-of-Plane Electromechanical Response of Monolayer Molybdenum Disulfide Measured by Piezoresponse Force Microscopy.

Two-dimensional (2D) materials have recently been theoretically predicted and experimentally confirmed to exhibit electromechanical coupling. Specifically, monolayer and few-layer molybdenum disulfide (MoS2) have been measured to be piezoelectric within the plane of their atoms. This work demonstrates and quantifies a nonzero out-of-plane electromechanical response of monolayer MoS2 and discusses its possible origins. A piezoresponse force microscope was used to measure the out-of-plane deformation of monolayer MoS2 on Au/Si and Al2O3/Si substrates. Using a vectorial background subtraction technique, we estimate the effective out-of-plane piezoelectric coefficient, d33eff, for monolayer MoS2 to be 1.03 ± 0.22 pm/V when measured on the Au/Si substrate and 1.35 ± 0.24 pm/V when measured on Al2O3/Si. This is on the same order as the in-plane coefficient d11 reported for monolayer MoS2. Interpreting the out-of-plane response as a flexoelectric response, the effective flexoelectric coefficient, µeff*, is estimated to be 0.10 nC/m. Analysis has ruled out the possibility of elastic and electrostatic forces contributing to the measured electromechanical response. X-ray photoelectron spectroscopy detected some contaminants on both MoS2 and its substrate, but the background subtraction technique is expected to remove major contributions from the unwanted contaminants. These measurements provide evidence that monolayer MoS2 exhibits an out-of-plane electromechanical response and our analysis offers estimates of the effective piezoelectric and flexoelectric coefficients.

Localized dielectric breakdown and antireflection coating in metal-oxide-semiconductor photoelectrodes.

Silicon-based photoelectrodes for solar fuel production have attracted great interest over the past decade, with the major challenge being silicon's vulnerability to corrosion. A metal-insulator-semiconductor architecture, in which an insulator film serves as a protection layer, can prevent corrosion but must also allow low-resistance carrier transport, generally leading to a trade-off between stability and efficiency. In this work, we propose and demonstrate a general method to decouple the two roles of the insulator by employing localized dielectric breakdown. This approach allows the insulator to be thick, which enhances stability, while enabling low-resistance carrier transport as required for efficiency. This method can be applied to various oxides, such as SiO2 and Al2O3. In addition, it is suitable for silicon, III-V compounds, and other optical absorbers for both photocathodes and photoanodes. Finally, the thick metal-oxide layer can serve as a thin-film antireflection coating, which increases light absorption efficiency.

A Low-Leakage Epitaxial High-κ Gate Oxide for Germanium Metal-Oxide-Semiconductor Devices.

Germanium (Ge)-based metal-oxide-semiconductor field-effect transistors are a promising candidate for high performance, low power electronics at the 7 nm technology node and beyond. However, the availability of high quality gate oxide/Ge interfaces that provide low leakage current density and equivalent oxide thickness (EOT), robust scalability, and acceptable interface state density (D(it)) has emerged as one of the most challenging hurdles in the development of such devices. Here we demonstrate and present detailed electrical characterization of a high-κ epitaxial oxide gate stack based on crystalline SrHfO3 grown on Ge (001) by atomic layer deposition. Metal-oxide-Ge capacitor structures show extremely low gate leakage, small and scalable EOT, and good and reducible D(it). Detailed growth strategies and postgrowth annealing schemes are demonstrated to reduce Dit. The physical mechanisms behind these phenomena are studied and suggest approaches for further reduction of D(it).

A Liquid Junction Photoelectrochemical Solar Cell Based on p-Type MeNH3PbI3 Perovskite with 1.05 V Open-Circuit Photovoltage.

A liquid junction photoelectrochemical (PEC) solar cell based on p-type methylammonium lead iodide (p-MeNH3PbI3) perovskite with a large open-circuit voltage is developed. MeNH3PbI3 perovskite is readily soluble or decomposed in many common solvents. However, the solvent dichloromethane (CH2Cl2) can be employed to form stable liquid junctions. These were characterized with photoelectrochemical cells with several redox couples, including I3(-)/I(-), Fc/Fc(+), DMFc/DMFc(+), and BQ/BQ(•-) (where Fc is ferrocene, DMFc is decamethylferrocene, BQ is benzoquinone) in CH2Cl2. The solution-processed MeNH3PbI3 shows cathodic photocurrents and hence p-type behavior. The difference between the photocurrent onset potential and the standard potential for BQ/BQ(•-) is 1.25 V, which is especially large for a semiconductor with a band gap of 1.55 eV. A PEC photovoltaic cell, with a configuration of p-MeNH3PbI3/CH2Cl2, BQ (2 mM), BQ(•-) (2 mM)/carbon, shows an open-circuit photovoltage of 1.05 V and a short-circuit current density of 7.8 mA/cm(2) under 100 mW/cm(2) irradiation. The overall optical-to-electrical energy conversion efficiency is 6.1%. The PEC solar cell shows good stability for 5 h under irradiation.