Harnessing Persistent Photocurrent in a 2D Semiconductor-Polymer Hybrid Structure: Electron Trapping and Fermi Level Modulation for Optoelectronic Memory.

Recently, 2D semiconductor-based optoelectronic memory has been explored to overcome the limitations of conventional von Neumann architectures by integrating optical sensing and data storage into one device. Persistent photocurrent (PPC), essential for optoelectronic memory, originates from charge carrier trapping according to the Shockley-Read-Hall (SRH) model in 2D semiconductors. The quasi-Fermi level position influences the activation of charge-trapping sites. However, the correlation between quasi-Fermi level modulations and PPC in 2D semiconductors has not been extensively studied. In this study, we demonstrate optoelectronic memory based on a 2D semiconductor-polymer hybrid structure and confirm that the underlying mechanism is charge trapping, as the SRH model explains. Under light illumination, electrons transfer from polyvinylpyrrolidone to p-type tungsten diselenide, resulting in high-level injection and majority carrier-type transitions. The quasi-Fermi level shifts upward with increasing temperature, improving PPC and enabling optoelectronic memory at 433 K. Our findings offer valuable insights into optimizing 2D semiconductor-based optoelectronic memory.

Monolithically Integrated Complementary Ferroelectric FET XNOR Synapse for the Binary Neural Network.

Neuromorphic computing, which mimics the structure and principles of the human brain, has the potential to facilitate the hardware implementation of next-generation artificial intelligence systems and process large amounts of data with very low power consumption. Among them, the XNOR synapse-based Binary Neural Network (BNN) has been attracting attention due to its compact neural network parameter size and low hardware cost. The previous XNOR synapse has drawbacks, such as a trade-off between cell density and accuracy. In this work, we show nonvolatile XNOR synapses with high density and accuracy using a monolithically stacked complementary ferroelectric field-effect transistor (C-FeFET) composed of a p-type Si MFMIS-FeFET at the bottom and a 3D stackable n-type Al:IZTO MFS-FeTFT, achieving 60F2 per cell (2C-FeFET). For adjusting the threshold voltage and improving the switching speed (100 ns) of n-type ferroelectric TFT, we employed a dual-gate configuration and a unique operation scheme, making it comparable to those of Si-based FeFETs. We performed array-level simulation with a 512 × 512 subarray size and a 3-bit flash ADC, demonstrating that the image recognition accuracies using the MNIST and CIFAR-10 data sets were increased by 3.17 and 14.07%, respectively, in comparison to other nonvolatile XNOR synapses. In addition, we performed system-level analysis on a 512 × 512 XNOR C-FeFET, exhibiting an outstanding throughput of 717.37 GOPS and an energy efficiency of 196.7 TOPS/W. We expect that our approach would contribute to the high-density memory systems, logic-in-memory technology, and hardware implementation of neural networks.

Sulfur isotope-based source apportionment and control mechanisms of PM2.5 sulfate in Seoul, South Korea during winter and early spring (2017-2020).

High level of particulate matter (PM) concentrations are a major environmental concern in Seoul, South Korea, especially during winter and early spring. Sulfate is a major component of PM and induces severe environmental pollution, such as acid precipitation. Previous studies have used numerical models to constrain the relative contributions of domestic and trans-boundary sources to PM2.5 sulfate concentration in South Korea. Because of the scarce measurement result of δ34S for PM2.5 sulfate in South Korea, poorly defined δ34S value of domestic sulfur sources, and no application of sulfur isotope fractionation during sulfate formation in previous observation-based studies, source apportionment results conducted by model studies have not been corroborated from independent chemical observations. Here, we examined the δ34S of PM2.5 in Seoul and domestic sulfur sources, and considered the sulfur isotope fractionation for accurate source apportionment constraint. Accordingly, domestic and trans-boundary sulfur sources accounted for approximately (16-32) % and (68-84) % of the sulfate aerosols in Seoul, respectively, throughout the winter and early spring of 2017-2020. Air masses passing through north-eastern China had relatively low sulfate concentrations, enriched δ34S, and a low domestic source contribution. Those passing through south-eastern China had relatively a high sulfate concentrations, depleted δ34S, and high domestic source contribution. Furthermore, elevated PM2.5 sulfate concentrations (>10 µg m-3) were exclusively associated with a weak westerly wind speed of <3 m s-1. From December 2019 to March 2020, Seoul experienced relatively low levels of PM2.5 sulfate, which might be attributed to favorable weather conditions rather than the effects of COVID-19 containment measures. Our results demonstrate the potential use of δ34S for accurate source apportionment and for identifying the crucial role of regional air mass transport and meteorological conditions in PM2.5 sulfate concentration. Furthermore, the data provided can be essential for relevant studies and policy-making in East Asia.

Extreme ultraviolet pellicle wrinkles influence on mask 3D effects: experimental demonstration.

Extreme ultraviolet (EUV) lithography uses reflective optics and a thick mask absorber, leading to mask 3D (M3D) effects. These M3D effects cause disparities in the amplitudes and phases of EUV mask diffractions, impacting mask imaging performance and reducing process yields. Our findings demonstrate that wrinkles in the EUV pellicle can exacerbate M3D effects. This imbalance results in critical dimension variation, image contrast loss, and pattern shift in mask images. Therefore, the use of a pellicle material with thermodynamic characteristics that minimize wrinkles when exposed to EUV rays is imperative.

Study on ZrSi2 as a Candidate Material for Extreme Ultraviolet Pellicles.

An extreme ultraviolet (EUV) pellicle is an ultrathin membrane at a stand-off distance from the reticle surface that protects the EUV mask from contamination during the exposure process. EUV pellicles must exhibit high EUV transmittance, low EUV reflectivity, and superior thermomechanical durability that can withstand the gradually increasing EUV source power. This study proposes an optimal range of optical constants to satisfy the EUV pellicle requirements based on the optical simulation results. Based on this, zirconium disilicide (ZrSi2), which is expected to satisfy the optical and thermomechanical requirements, was selected as the EUV pellicle candidate material. An EUV pellicle composite comprising a ZrSi2 thin film deposited via co-sputtering was fabricated, and its thermal, optical, and mechanical properties were evaluated. The emissivity increased with an increase in the thickness of the ZrSi2 thin film. The measured EUV transmittance (92.7%) and reflectivity (0.033%) of the fabricated pellicle satisfied the EUV pellicle requirements. The ultimate tensile strength of the pellicle was 3.5 GPa. Thus, the applicability of the ZrSi2 thin film as an EUV pellicle material was verified.

Fossil and non-fossil sources of the carbonaceous component of PM2.5 in forest and urban areas.

Atmospheric particulate matter (PM2.5) can damage human health. Biogenic organic compounds emitted from trees may increase the concentration of PM2.5 via formation of secondary aerosols. Therefore, the role of biogenic emissions in PM2.5 formation and the sources of PM2.5 need to be investigated. Dual carbon isotope and levoglucosan analyses are powerful tools to track the sources of total carbon (TC) in PM2.5. We collected a total of 47 PM2.5 samples from 2019 to 2020 inside a pine forest and in urban areas in South Korea. The average δ13C and Δ14C of TC in PM2.5 at the Taehwa Research Forest (TRF) were - 25.7 and - 380.7‰, respectively, which were not significantly different from those collected at Seoul National University (SNU) in urban areas. Contribution of fossil fuel, C3-, and C4- plants to carbonaceous component of PM2.5 were 52, 27, and 21% at SNU, whereas those were 46, 35, and 19% at TRF, respectively. The biomass burning tracer, levoglucosan, was most abundant in winter and correlated with the contribution of C4 plants derived carbon. Results indicate that biogenic aerosols emitted from trees is less likely to be an important source of PM2.5 and that trees can act as a bio-filter to reduce PM2.5.

Near-field infrared nanoscopic study of EUV- and e-beam-exposed hydrogen silsesquioxane photoresist.

This article presents a technique of scattering-type scanning near-field optical microscopy (s-SNOM) based on scanning probe microscopy as a nanoscale-resolution chemical visualization technique of the structural changes in photoresist thin films. Chemical investigations were conducted in the nanometer regime by highly concentrated near-field infrared on the sharp apex of the metal-coated atomic force microscopy (AFM) tip. When s-SNOM was applied along with Fourier transform infrared spectroscopy to characterize the extreme UV- and electron-beam (e-beam)-exposed hydrogen silsesquioxane films, line and space patterns of half-pitch 100, 200, 300, and 500 nm could be successfully visualized prior to pattern development in the chemical solutions. The linewidth and line edge roughness values of the exposed domains obtained by s-SNOM were comparable to those extracted from the AFM and scanning electron microscopy images after development. The chemical analysis capabilities provided by s-SNOM provide new analytical opportunities that are not possible with traditional e-beam-based photoresist measurement, thus allowing information to be obtained without interference from non-photoreaction processes such as wet development.

Effect of wrinkles on extreme ultraviolet pellicle reflectivity and local critical dimension.

Extreme ultraviolet (EUV) pellicles must have an EUV reflectance (EUVR) below 0.04% to prevent the reduction of critical dimension (CD). However, pellicle wrinkles cause localized CD variation by locally amplifying the EUVR. This study demonstrates that wrinkles can increase the pellicle's EUVR by approximately four times, and the CD drop depends on the relative position of the reflected light from the wrinkle to the 0th- or 1st-order diffracted light. The CD decreases by 6 nm. Therefore, even if the pellicle satisfies the requirement for the EUVR, we need to tightly control the generation of wrinkles to suppress CD variation during the entire exposure process.

Investigation of the Resistivity and Emissivity of a Pellicle Membrane for EUV Lithography.

A pellicle is a thin membrane structure that protects an extreme ultraviolet (EUV) mask from contamination during the exposure process. However, its limited transmittance induces unwanted heating owing to the absorption of EUV photons. The rupture of the EUV pellicle can be avoided by improving its thermal stability, which is achieved by improving the emissivity of the film. However, the emissivity data for thin films are not easily available in the literature, and its value is very sensitive to thickness. Therefore, we investigated the dependence of emissivity on structural parameters, such as thickness, surface roughness, and grain size. We found a correlation between resistivity and emissivity using theoretical and experimental approaches. By changing the grain size of the Ru thin film, the relationship between resistivity and emissivity was experimentally verified and confirmed using the Lorentz-Drude model. Finally, we present a method to develop an EUV pellicle with better thermal stability that can withstand high-power EUV light sources.

Investigating the Degradation of EUV Transmittance of an EUV Pellicle Membrane.

The extreme ultraviolet (EUV) pellicle is a freestanding membrane that protects EUV masks from particle contamination during EUV exposure. Although a high EUV transmittance of the pellicle is required to minimize the loss of throughput, the degradation of EUV transmittance during the extended exposure of the pellicle has been recently reported. This may adversely affect the throughput of the lithography process. However, the cause of this phenomenon has not yet been clarified. Therefore, we investigated the cause of the degradation in the EUV transmittance by observing the compositional change when the Ru/SiNx pellicle composite was heated in an emulated EUV scanner environment. The Ru thin film that was deposited at high pressure had more void networks but was not oxidized, whereas the SiNx thin film was oxidized after heating. This was because the void network in the Ru thin film served as a preferential diffusion path for oxygen and caused oxidation of the SiNx thin film. It was confirmed that the degradation of the EUV transmittance was due to the oxidation of SiNx. The results verified the effect of diffusivity in the thin film due to the void network on oxidation and EUV transmittance.

Microstructures of HfOx Films Prepared via Atomic Layer Deposition Using La(NO3)3·6H2O Oxidants.

Hafnium oxide (HfOx) films have a wide range of applications in solid-state devices, including metal-oxide-semiconductor field-effect transistors (MOSFETs). The growth of HfOx films from the metal precursor tetrakis(ethylmethylamino) hafnium with La(NO3)3·6H2O solution (LNS) as an oxidant was investigated. The atomic layer deposition (ALD) conditions were optimized, and the chemical state, surface morphology, and microstructure of the prepared films were characterized. Furthermore, to better understand the effects of LNS on the deposition process, HfOx films deposited using a conventional oxidant (H2O) were also prepared. The ALD process using LNS was observed to be self-limiting, with an ALD temperature window of 200-350 °C and a growth rate of 1.6 Å per cycle, two times faster than that with H2O. HfOx films deposited using the LNS oxidant had smaller crystallites than those deposited using H2O, as well as more suboxides or defects because of the higher number of grain boundaries. In addition, there was a difference in the preferred orientations of the HfOx films deposited using LNS and H2O, and consequently, a difference in surface energy. Finally, a film growth model based on the surface energy difference was proposed to explain the observed growth rate and crystallite size trends.

Antarctic surface temperature and elevation during the Last Glacial Maximum.

Water-stable isotopes in polar ice cores are a widely used temperature proxy in paleoclimate reconstruction, yet calibration remains challenging in East Antarctica. Here, we reconstruct the magnitude and spatial pattern of Last Glacial Maximum surface cooling in Antarctica using borehole thermometry and firn properties in seven ice cores. West Antarctic sites cooled ~10°C relative to the preindustrial period. East Antarctic sites show a range from ~4° to ~7°C cooling, which is consistent with the results of global climate models when the effects of topographic changes indicated with ice core air-content data are included, but less than those indicated with the use of water-stable isotopes calibrated against modern spatial gradients. An altered Antarctic temperature inversion during the glacial reconciles our estimates with water-isotope observations.

Low Temperature Thermal Atomic Layer Deposition of Aluminum Nitride Using Hydrazine as the Nitrogen Source.

Aluminum nitride (AlN) thin films were grown using thermal atomic layer deposition in the temperature range of 175-350 °C. The thin films were deposited using trimethyl aluminum (TMA) and hydrazine (N2H4) as a metal precursor and nitrogen source, respectively. Highly reactive N2H4, compared to its conventionally used counterpart, ammonia (NH3), provides a higher growth per cycle (GPC), which is approximately 2.3 times higher at a deposition temperature of 300 °C and, also exhibits a low impurity concentration in as-deposited films. Low temperature AlN films deposited at 225 °C with a capping layer had an Al to N composition ratio of 1:1.1, a close to ideal composition ratio, with a low oxygen content (7.5%) while exhibiting a GPC of 0.16 nm/cycle. We suggest that N2H4 as a replacement for NH3 is a good alternative due to its stringent thermal budget.

A Comprehensive Study on the Effect of TiN Top and Bottom Electrodes on Atomic Layer Deposited Ferroelectric Hf0.5Zr0.5O2 Thin Films.

The discovery of ferroelectricity in HfO2-based materials in 2011 provided new research directions and opportunities. In particular, for atomic layer deposited Hf0.5Zr0.5O2 (HZO) films, it is possible to obtain homogenous thin films with satisfactory ferroelectric properties at a low thermal budget process. Based on experiment demonstrations over the past 10 years, it is well known that HZO films show excellent ferroelectricity when sandwiched between TiN top and bottom electrodes. This work reports a comprehensive study on the effect of TiN top and bottom electrodes on the ferroelectric properties of HZO thin films (10 nm). Investigations showed that during HZO crystallization, the TiN bottom electrode promoted ferroelectric phase formation (by oxygen scavenging) and the TiN top electrode inhibited non-ferroelectric phase formation (by stress-induced crystallization). In addition, it was confirmed that the TiN top and bottom electrodes acted as a barrier layer to hydrogen diffusion into the HZO thin film during annealing in a hydrogen-containing atmosphere. These features make the TiN electrodes a useful strategy for improving and preserving the ferroelectric properties of HZO thin films for next-generation memory applications.

Performance of Extreme Ultraviolet Coherent Scattering Microscope.

For the successful implementation of extreme ultraviolet lithography (EUVL) into high-volume manufacturing, the development of a novel structure mask for resolution improvement is essential. In this paper, coherent scattering microscopy (CSM) is introduced as an actinic metrology technique based on coherent diffractive imaging (CDI) for EUV mask development. CDI reconstructs the mask image using diffraction patterns from the mask through mathematical calculations. CSM can analyze details of an EUV mask such as its diffraction efficiency and phase information.

Thickness-dependent and anisotropic thermal conductivity of black phosphorus nanosheets.

Thickness effects on thermal conductivities of black phosphorus nanosheets, which are anisotropic in the zigzag and armchair planar directions, are experimentally and theoretically investigated in the thickness range of 13 to 48 nm. The thermal conductivities decrease with the thickness, decreasing from 13 to 8 W m-1 K-1 in the zigzag direction and from 10 to 6 W m-1 K-1 in the armchair direction at 300 K, respectively. The anisotropic thermal conductivities, regardless of the thickness, might result from the anisotropic phonon velocity arising from the hinge-like structure. The surface-driven suppression of the thermal conductivities at a nanometer scale is remarkable for a wide temperature range of 100 to 300 K due to phonon-boundary scattering, while the thermal conductivity becomes less dependent on the thickness at higher temperatures above 300 K, owing to the dominant phonon-phonon scattering.

Variations in bacterial and archaeal communities along depth profiles of Alaskan soil cores.

Understating the microbial communities and ecological processes that influence their structure in permafrost soils is crucial for predicting the consequences of climate change. In this study we investigated the bacterial and archaeal communities along depth profiles of four soil cores collected across Alaska. The bacterial and archaeal diversity (amplicon sequencing) overall decreased along the soil depth but the depth-wise pattern of their abundances (qPCR) varied by sites. The community structure of bacteria and archaea displayed site-specific pattern, with a greater role of soil geochemical characteristics rather than soil depth. In particular, we found significant positive correlations between methane trapped in cores and relative abundance of methanogenic archaeal genera, indicating a strong association between microbial activity and methane production in subsurface soils. We observed that bacterial phylogenetic community assembly tended to be more clustered in surface soils than in deeper soils. Analyses of phylogenetic community turnover among depth profiles across cores indicated that the relative influence of deterministic and stochastic processes was mainly determined by soil properties rather than depth. Overall, our findings emphasize that the vertical distributions of bacterial and archaeal communities in permafrost soils are to a large extent determined by the variation in site-specific soil properties.

High-Precision Measurement of N2O Concentration in Ice Cores.

Atmospheric nitrous oxide (N2O) is a greenhouse gas and ozone-depleting substance whose emissions are substantially perturbed by current human activities. Although air trapped in polar ice cores can provide direct information about N2O evolution, analytical precision was not previously sufficient for high temporal resolution studies. In this work, we present a highly improved analytical technique with which to study N2O concentrations in ancient-air-trapped ice cores. We adopt a melt-refreezing method to extract air and use a gas chromatography-electron capture detector (GC-ECD) to determine N2O concentrations. The GC conditions are optimized to improve the sensitivity for detecting N2O. Retrapped N2O in ice during the extraction procedure is precisely analyzed and corrected. We confirmed our results using data from the Styx Glacier ice core in Antarctica by comparing them with the results of a dry-extraction method. The precision estimated from the pooled standard deviation of replicated measurements of the Styx ice core was 1.5 ppb for ∼20 g of ice, a smaller sample of ice than was used in previous studies, showing a significant improvement in precision. Our preliminary results from the Styx Glacier ice core samples have the potential to define small N2O variations (a few parts per billion) at centennial time scales.

Coherent scattering microscopy as an effective inspection tool for analyzing performance of phase shift mask.

The imaging performance of a half-tone phase shift mask (PSM) has been analyzed using coherent scattering microscopy (CSM), which allows analysis of the actinic characteristics of an extreme ultraviolet (EUV) mask such as its reflectivity, diffraction efficiency, and phase information. This paper presents the 1st experimental result showing the effect of 180° phase difference between the absorber and reflector in EUV mask. This reveals that a PSM offers a 46% improvement in 1st/0th diffraction efficiency and 14% improvement in image contrast when compared to a binary intensity mask (BIM). The horizontal-vertical critical dimension (H-V CD) bias is also reduced by 1.37 nm at 22 nm line and space (L/S) patterns. Since the performance of PSM can be evaluated without a wafer patterning process, CSM is expected to be a useful inspection tool for the development of novel EUV masks.