Room-temperature spin injection across a chiral perovskite/III-V interface.

Spin accumulation in semiconductor structures at room temperature and without magnetic fields is key to enable a broader range of optoelectronic functionality1. Current efforts are limited owing to inherent inefficiencies associated with spin injection across semiconductor interfaces2. Here we demonstrate spin injection across chiral halide perovskite/III-V interfaces achieving spin accumulation in a standard semiconductor III-V (AlxGa1-x)0.5In0.5P multiple quantum well light-emitting diode. The spin accumulation in the multiple quantum well is detected through emission of circularly polarized light with a degree of polarization of up to 15 ± 4%. The chiral perovskite/III-V interface was characterized with X-ray photoelectron spectroscopy, cross-sectional scanning Kelvin probe force microscopy and cross-sectional transmission electron microscopy imaging, showing a clean semiconductor/semiconductor interface at which the Fermi level can equilibrate. These findings demonstrate that chiral perovskite semiconductors can transform well-developed semiconductor platforms into ones that can also control spin.

Investigation of Sub-Bandgap Emission and Unexpected n-Type Behavior in Undoped Polycrystalline CdSexTe1-x.

Se alloying has enabled significantly higher carrier lifetimes and photocurrents in CdTe solar cells, but these benefits can be highly dependent on CdSexTe1-x processing. This work evaluates the optoelectronic, chemical, and electronic properties of thick (3 µm) undoped CdSexTe1-x of uniform composition and varied processing conditions (CdSexTe1-x evaporation rate, CdCl2 anneal, Se content) chosen to reflect various standard device processing conditions. Sub-bandgap defect emission is observed, which increased as Se content increased and with "GrV-optimized CdCl2" (i.e., CdCl2 anneal conditions used for group-V-doped devices). Low carrier lifetime is found for GrV-optimized CdCl2, slow CdSexTe1-x deposition, and low-Se films. Interestingly, all films (including CdTe control) exhibited n-type behavior, where electron density increased with Se up to an estimated ≈1017 cm-3. This behavior appears to originate during the CdCl2 anneal, possibly from Se diffusion leading to anion vacancy (e.g., VSe, VTe) and ClTe generation.

Operando Characterizations of Light-Induced Junction Evolution in Perovskite Solar Cells.

Light-induced performance changes in metal halide perovskite solar cells (PSCs) have been studied intensively over the last decade, but little is known about the variation in microscopic optoelectronic properties of the perovskite heterojunctions in a completed device during operation. Here, we combine Kelvin probe force microscopy and transient reflection spectroscopy techniques to spatially resolve the evolution of junction properties during the operation of metal-halide PSCs and study the light-soaking effect. Our analysis showed a rise of an electric field at the hole-transport layer side, convoluted with a more reduced interfacial recombination rate at the electron-transport layer side in the PSCs with an n-i-p structure. The junction evolution is attributed to the effects of ion migration and self-poling by built-in voltage. Device performances are correlated with the changes of electrostatic potential distribution and interfacial carrier dynamics. Our results demonstrate a new route for studying the complex operation mechanism in PSCs.

Initial results of the meteorological data from the first 325 sols of the Tianwen-1 mission.

As the Zhurong rover landed on the surface of Mars in 2021, it began a months-long collection of Mars data. Equipped with highly sensitive sensors, Zhurong is capable of being a meteorological station at the surface of Mars. The Mars Climate Station, one of the onboard sensors with high sensitivity, helps the Tianwen-1 lander to collect meteorological data at the Martian surface, via which the air temperature, atmospheric pressure, wind speed and direction are measured. In this paper, we present results of surface pressure, air temperature and wind data from the Mars Climate Station at Zhurong's landing site. The data is collected in 176 solar days out of the entire rover's mission time, 325 solar days. We use a trigonometric function to fit the relationship between the solar longitude (Ls) and the pressure, after which we compare the results with those of Viking I. Our analysis of the temperature shows that seasonal evolution is similar to the patterns concluded in previous Mars missions at different landing sites. We discover that wind speed appears the maximum in early summer near Zhurong's landing site, and analyze the occurrence of dust storms by combining the data of wind and temperature. Our results provide some evidence of the seasonal changes in meteorological pattern at Tianwen-1's landing site, south of Utopia Planitia. With the mission ongoing further, more results are expected in the future.

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.

Atomic threshold-switching enabled MoS2 transistors towards ultralow-power electronics.

Power dissipation is a fundamental issue for future chip-based electronics. As promising channel materials, two-dimensional semiconductors show excellent capabilities of scaling dimensions and reducing off-state currents. However, field-effect transistors based on two-dimensional materials are still confronted with the fundamental thermionic limitation of the subthreshold swing of 60 mV decade-1 at room temperature. Here, we present an atomic threshold-switching field-effect transistor constructed by integrating a metal filamentary threshold switch with a two-dimensional MoS2 channel, and obtain abrupt steepness in the turn-on characteristics and 4.5 mV decade-1 subthreshold swing (over five decades). This is achieved by using the negative differential resistance effect from the threshold switch to induce an internal voltage amplification across the MoS2 channel. Notably, in such devices, the simultaneous achievement of efficient electrostatics, very small sub-thermionic subthreshold swings, and ultralow leakage currents, would be highly desirable for next-generation energy-efficient integrated circuits and ultralow-power applications.

Effect of Water Concentration in LiPF6-Based Electrolytes on the Formation, Evolution, and Properties of the Solid Electrolyte Interphase on Si Anodes.

A trace amount of water in an electrolyte is one of the factors detrimental to the electrochemical performance of silicon (Si)-based lithium-ion batteries that adversely affect the formation and evolution of the solid electrolyte interphase (SEI) on Si-based anodes and change its properties. Thus far, a lack of fundamental and mechanistic understanding of SEI formation, evolution, and properties in the presence of water has inhibited efforts to stabilize the SEI for improved electrochemical performance. Thus, we investigated the SEI formed in a Gen2 electrolyte (1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 3:7 wt %, water content: <10 ppm) with and without additional water (50 ppm) at varying potentials (1.0, 0.5, 0.2, and 0.01 V vs Li/Li+). The impact of additional water on the morphological, (electro)chemical, and structural properties of SEI was studied using microscopic (atomic force microscopy and scanning spreading resistance microscopy) and spectroscopic (X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry) techniques. The SEI exhibits both potential- and water concentration-dependent trends in its morphology and chemical composition. The presence of additional water in the electrolyte causes parasitic reactions, which onset at ∼1.0 V, resulting in a reduction of electrolyte components and result in the formation of an insulating, fluorophosphate-rich SEI. In addition, hydrolysis of LiPF6 creates hydrofluoric acid, which reacts with the surface oxide layer on the Si electrode, leading to a pitted and inhomogeneous SEI structure.

Improved Performance of SRAM-Based True Random Number Generator by Leveraging Irradiation Exposure.

Encryption is an important step for secure data transmission, and a true random number generator (TRNG) is a key building block in many encryption algorithms. Static random-access memory (SRAM) chips can be easily available sources of true random numbers, benefiting from noisy SRAM cells whose start-up values flip between different power-on cycles. Embarking from this phenomenon, a novel performance (i.e., randomness and throughput) improvement method of SRAM-based TRNG is proposed, and its implementation can be divided into two phases: irradiation exposure and hardware postprocessing. As the randomness of original SRAM power-on values is fairly low, ionization irradiation is utilized to enhance its randomness, and the min-entropy can increase from about 0.03 to above 0.7 in the total ionizing irradiation (TID) experiments. Additionally, while the data remanence effect hampers obtaining random bitstreams with high speed, the ionization irradiation can also weaken this impact and improve the throughput of TRNG. In the hardware postprocessing stage, Secure Hash Algorithm 256 (SHA-256) is implemented on a Field Programmable Gate Array (FPGA) with clock frequency of 200 MHz. It can generate National Institute of Standards and Technology (NIST) SP 800-22 compatible true random bitstreams with throughput of 178 Mbps utilizing SRAM chip with 1 Mbit memory capacity. Furthermore, according to different application scenarios, the throughput can be widely scalable by adjusting clock frequency and SRAM memory capacity, which makes the novel TRNG design applicable for various Internet of Things (IOT) devices.

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.

Carrier-Transport Study of Gallium Arsenide Hillock Defects.

Single-crystalline gallium arsenide (GaAs) grown by various techniques can exhibit hillock defects on the surface when sub-optimal growth conditions are employed. The defects act as nonradiative recombination centers and limit solar cell performance. In this paper, we applied near-field transport imaging to study hillock defects in a GaAs thin film. On the same defects, we also performed near-field cathodoluminescence, standard cathodoluminescence, electron-backscattered diffraction, transmission electron microscopy, and energy-dispersive X-ray spectrometry. We found that the luminescence intensity around the hillock area is two orders of magnitude lower than on the area without hillock defects in the millimeter region, and the excess carrier diffusion length is degraded by at least a factor of five with significant local variation. The optical and transport properties are affected over a significantly larger region than the observed topography and crystallographic and chemical compositions associated with the defect.

Mechanical Properties and Chemical Reactivity of Li xSiO y Thin Films.

Silicon (Si) is a commonly studied candidate material for next-generation anodes in Li-ion batteries. A native oxide SiO2 on Si is often inevitable. However, it is not clear if this layer has a positive or negative effect on the battery performance. This understanding is complicated by the lack of knowledge about the physical properties of the SiO2 lithiation products and by the convolution of chemical and electrochemical effects during the anode lithiation process. In this study, Li xSiO y thin films as model materials for lithiated SiO2 were deposited by magnetron sputtering at ambient temperature, with the goal of (1) decoupling chemical reactivity from electrochemical reactivity and (2) evaluating the physical and electrochemical properties of Li xSiO y. X-ray photoemission spectroscopy analysis of the deposited thin films demonstrate that a composition close to previous experimental reports of lithiated native SiO2 can be achieved through sputtering. Our density functional theory calculations also confirm that the possible phases formed by lithiating SiO2 are very close to the measured film compositions. Scanning probe microscopy measurements show that the mechanical properties of the film are strongly dependent on lithium concentration, with a ductile behavior at a higher Li content and a brittle behavior at a lower Li content. The chemical reactivity of the thin films was investigated by measuring the AC impedance evolution, suggesting that Li xSiO y continuously reacts with the electrolyte, in part because of the high electronic conductivity of the film determined from solid-state impedance measurements. The electrochemical cycling data of the sputter-deposited Li xSiO y/Si films also suggest that Li xSiO y is not beneficial in stabilizing the Si anode surface during battery operation, despite its favorable mechanical properties.

Mechanical Properties and Chemical Reactivity of LixSiOy Thin Films.

Silicon (Si) is a commonly studied candidate material for next-generation anodes in Li-ion batteries. A native oxide SiO2 on Si is often inevitable. However, it is not clear if this layer has positive or negative effect on the battery performance. This understanding is complicated by the lack of knowledge about the physical properties, and by convolution of chemical and electrochemical effects during the anode lithiation process. In this study, LixSiOy thin films as model materials for lithiated SiO2 were deposited by magnetron sputtering at ambient temperature, with the goal of 1) decoupling chemical reactivity from electrochemical reactivity, and 2) evaluating the physical and electrochemical properties of LixSiOy. XPS analysis of the deposited thin films demonstrate that a composition close to previous experimental reports of lithiated native SiO2, can be achieved through sputtering. Our density functional theory calculations also confirm that possible phases formed by lithiating SiO2 are very close to the measured film compositions. Scanning probe microscopy measurements show the mechanical properties of the film are strongly dependent on lithium concentration, with ductile behavior and higher Li content and brittle behavior at lower Li content. Chemical reactivity of the thin films was investigated by measuring AC impedance evolution, suggesting that LixSiOy continuously reacts with electrolyte, in part due to high electronic conductivity of the film determined from solid state impedance measurements. Electrochemical cycling data of sputter deposited LixSiOy/Si films also suggest that LixSiOy is not beneficial in stabilizing the Si anode surface during battery operation, despite its favorable mechanical properties.

MoS2 Negative-Capacitance Field-Effect Transistors with Subthreshold Swing below the Physics Limit.

The Boltzmann distribution of electrons induced fundamental barrier prevents subthreshold swing (SS) from less than 60 mV dec-1 at room temperature, leading to high energy consumption of MOSFETs. Herein, it is demonstrated that an aggressive introduction of the negative capacitance (NC) effect of ferroelectrics can decisively break the fundamental limit governed by the "Boltzmann tyranny". Such MoS2 negative-capacitance field-effect transistors (NC-FETs) with self-aligned top-gated geometry demonstrated here pull down the SS value to 42.5 mV dec-1 , and simultaneously achieve superior performance of a transconductance of 45.5 µS µm and an on/off ratio of 4 × 106 with channel length less than 100 nm. Furthermore, the inserted HfO2 layer not only realizes a stable NC gate stack structure, but also prevents the ferroelectric P(VDF-TrFE) from fatigue with robust stability. Notably, the fabricated MoS2 NC-FETs are distinctly different from traditional MOSFETs. The on-state current increases as the temperature decreases even down to 20 K, and the SS values exhibit nonlinear dependence with temperature due to the implementation of the ferroelectric gate stack. The NC-FETs enable fundamental applications through overcoming the Boltzmann limit in nanoelectronics and open up an avenue to low-power transistors needed for many exciting long-endurance portable consumer products.

Steep-Slope WSe2 Negative Capacitance Field-Effect Transistor.

P-type two-dimensional steep-slope negative capacitance field-effect transistors are demonstrated for the first time with WSe2 as channel material and ferroelectric hafnium zirconium oxide in gate dielectric stack. F4-TCNQ is used as p-type dopant to suppress electron leakage current and to reduce Schottky barrier width for holes. WSe2 negative capacitance field-effect transistors with and without internal metal gate structures and the internal field-effect transistors are compared and studied. Significant SS reduction is observed in WSe2 negative capacitance field-effect transistors by inserting the ferroelectric hafnium zirconium oxide layer, suggesting the existence of internal amplification (∼10) due to the negative capacitance effect. Subthreshold slope less than 60 mV/dec (as low as 14.4 mV/dec) at room temperature is obtained for both forward and reverse gate voltage sweeps. Negative differential resistance is observed at room temperature on WSe2 negative capacitance field-effect-transistors as the result of negative capacitance induced negative drain-induced-barrier-lowering effect.

Steep-slope hysteresis-free negative capacitance MoS2 transistors.

The so-called Boltzmann tyranny defines the fundamental thermionic limit of the subthreshold slope of a metal-oxide-semiconductor field-effect transistor (MOSFET) at 60 mV dec-1 at room temperature and therefore precludes lowering of the supply voltage and overall power consumption 1,2 . Adding a ferroelectric negative capacitor to the gate stack of a MOSFET may offer a promising solution to bypassing this fundamental barrier 3 . Meanwhile, two-dimensional semiconductors such as atomically thin transition-metal dichalcogenides, due to their low dielectric constant and ease of integration into a junctionless transistor topology, offer enhanced electrostatic control of the channel 4-12 . Here, we combine these two advantages and demonstrate a molybdenum disulfide (MoS2) two-dimensional steep-slope transistor with a ferroelectric hafnium zirconium oxide layer in the gate dielectric stack. This device exhibits excellent performance in both on and off states, with a maximum drain current of 510 µA µm-1 and a sub-thermionic subthreshold slope, and is essentially hysteresis-free. Negative differential resistance was observed at room temperature in the MoS2 negative-capacitance FETs as the result of negative capacitance due to the negative drain-induced barrier lowering. A high on-current-induced self-heating effect was also observed and studied.

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.

Do grain boundaries dominate non-radiative recombination in CH3NH3PbI3 perovskite thin films?

Here, we examine grain boundaries (GBs) with respect to non-GB regions (grain surfaces (GSs) and grain interiors (GIs)) in high-quality micrometer-sized perovskite CH3NH3PbI3 (or MAPbI3) thin films using high-resolution confocal fluorescence-lifetime imaging microscopy in conjunction with kinetic modeling of charge-transport and recombination processes. We show that, contrary to previous studies, GBs in our perovskite MAPbI3 thin films do not lead to increased recombination but that recombination in these films happens primarily in the non-GB regions (i.e., GSs or GIs). We also find that GBs in these films are not transparent to photogenerated carriers, which is likely associated with a potential barrier at GBs. Even though GBs generally display lower luminescence intensities than GSs/GIs, the lifetimes at GBs are no worse than those at GSs/GIs, further suggesting that GBs do not dominate non-radiative recombination in MAPbI3 thin films.

Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar Perovskite Solar Cells.

Lead thiocyanate in the perovskite precursor can increase the grain size of a perovskite thin film and reduce the conductivity of the grain boundaries, leading to perovskite solar cells with reduced hysteresis and enhanced fill factor. A planar perovskite solar cell with grain boundary and interface passivation achieves a steady-state efficiency of 18.42%.

Square-Centimeter Solution-Processed Planar CH3NH3PbI3 Perovskite Solar Cells with Efficiency Exceeding 15.

The preparation of uniform, high-crystallinity planar perovskite films with high-aspect-ratio grains over a square-inch area is demonstrated. The best power conversion efficiency (PCE) of 16.3% (stabilized output of ≈15.6%) is obtained for a planar perovskite solar cell (PSC) with 1.2 cm2 active area, and the PCE jumps to 18.3% (stabilized output of ≈17.5%) for a PSC with a 0.12 cm2 active area.