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At least 1,369 records · Page 76

Kinetics of moisture-induced phase transformation in inorganic halide perovskite

The high-temperature (high-T) phase of cesium lead iodide (CsPbI 3 ) presents great promise for photovoltaic applications; however, exposure to ambient moisture at room temperature transforms it into its less-desirable low-temperature (low-T) phase with a larger band gap. While there have been theoretical predictions on the influence of moisture level on the phase transformation kinetics, the corresponding quantitative experimental evidence has remained limited. Tracking CsPbI 3 phase transformation under controlled relative humidity (RH), we find that rising RH increases the nucleation rate of low-T CsPbI 3 exponentially, but has a weak effect on its growth. The overall transformation is nucleation limited, with higher RH leading to a lower nucleation barrier. Finally, we find that heating between 40°C and 80°C facilitates water desorption and suppresses phase transformation. Our findings elucidate the relationship between moisture and the phase energetics of CsPbI 3 , which can serve as references for thin film applications of CsPbI 3 and future designs of stable photovoltaics systems.

36 MATERIALS SCIENCE↗

Accelerated aging test of new plastic scintillators

Fogging in plastic scintillators is a degradation mechanism that reduces light collection efficiency. In an effort to reduce maintenance costs, multiple groups have attempted to understand and prevent this problem by changing plastic compositions and system level designs. New formulations have been produced that are promising with respect to fogging resistance. In this paper, we study a variety of new compositions by subjecting them to an accelerated aging experiment with varying temperature and humidity profiles. Compositions are analyzed for their resistance to degradation after saturation periods, with those containing polymethyl methacrylate and divinyl benzene being the most promising. Pulse height spectra revealed that after environmental aging, many of the samples suffered a reduction in light yield to different degrees, a result that could be due to heating of the samples and may be prevented by further production optimization.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Pool boiling critical heat flux studies of accident tolerant fuel cladding materials

Pool boiling experiments have been performed at atmospheric pressure on potential accident tolerant fuel (ATF) cladding materials (Zirlo®, Cr coated Zirlo®, FeCrAl coated Zirlo®, and monolithic SiC) to evaluate the Critical Heat Flux (CHF) points. Corrosion resistant coatings of Cr and FeCrAl alloy were deposited on flat Zirlo® samples using cold spray technology. The as-prepared samples after uniform surface polishing were subjected to autoclave tests at 360 °C water and 18.6 MPa for 360 h to simulate prototypic corrosion of the ATF cladding materials in LWR normal operation. Surface characteristics potentially influencing CHF such as surface morphology, roughness, static contact angle, and surface chemistry were characterized using a suite of characterization methods including scanning electron microscopy, 3D optical profilometry, optical contact angle measurements, and x-ray photoelectron spectroscopy (XPS). Thermo-physical properties of the samples such as density, thermal conductivity, and heat capacity were measured by differential scanning calorimetry and laser flash thermal diffusivity measurement. FeCrAl coatings showed CHF values comparable to bare Zirlo® samples, while slightly lower CHF values were observed for Cr coated samples and bulk SiC flats (produced by chemical vapor deposition, CVD). As-deposited Cr coatings showed 67% higher CHF than the as-polished Cr coatings due to its higher surface roughness level. The autoclave testing for the prepared samples generally increased the CHF except for the surface polished Cr coatings. Similar CHF values of bare Zirlo®, FeCrAl coating, and CVD SiC samples were observed after autoclave test but there were negligible change CHF of Cr coatings. XPS studies indicated that the formation or deposition of a few monolayers of hydrophobic carbonaceous species on surface can affect CHF values. The trends in CHF data are discussed in terms of evolution of the surface characteristics of the ATF materials.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Selective Transfer of Rotationally Commensurate MoS 2 from an Epitaxially Grown van der Waals Heterostructure

We report that large-scale synthesis of high-quality two-dimensional (2D) semiconductors is critical for their incorporation in emerging electronic and optoelectronic technologies. In particular, chemical vapor deposition (CVD) of transition-metal dichalcogenides (TMDs) via van der Waals epitaxy on epitaxial graphene (EG) leads to rotationally commensurate TMDs in contrast to randomly aligned TMDs grown on amorphous oxide substrates. However, the interlayer coupling between TMDs and EG hinders the investigation and utilization of the intrinsic electronic properties of the resulting TMDs, thus requiring their isolation from the EG growth substrate. To address this issue, we report here a technique for selectively transferring monolayer molybdenum disulfide (MoS 2 ) from CVD-grown MoS 2 -EG van der Waals heterojunctions using copper (Cu) adhesion layers. The choice of Cu as the adhesion layer is motivated by density functional theory calculations that predict the preferential binding of monolayer MoS 2 to Cu in contrast to graphene. Atomic force microscopy and optical spectroscopy confirm the large-scale transfer of rotationally commensurate MoS 2 onto SiO 2 /Si substrates without cracks, wrinkles, or residues. Furthermore, the transferred MoS 2 shows high performance in field-effect transistors with mobilities of up to 30 cm 2 /V s and on/off ratios of up to 10 6 at room temperature. Lastly, this transfer technique can likely be generalized to other TMDs and related 2D materials grown on EG, thus offering a broad range of benefits in nanoelectronic, optoelectronic, and photonic applications.

36 MATERIALS SCIENCE↗

High-Throughput Characterization of (Fe x Co 1–x ) 3 O 4 Thin-Film Composition Spreads

In this study, thin-film continuous composition spreads of Fe–Co–O were fabricated by reactive cosputtering from elemental Fe and Co targets in reactive Ar/O 2 atmosphere using deposition temperatures ranging from 300 to 700 °C. Fused silica and platinized Si/SiO 2 strips were used as substrates. Ti and Ta were investigated as adhesion layer for Pt and the fabrication of the Fe–Co–O films. The thin-film composition spreads were characterized by high-throughput electron-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, and optical transmission spectroscopy. The Fe-content ranged from 28 to 72 at. %. The spinel phases Fe 2 CoO 4 and FeCo 2 O 4 could be synthesized and stabilized at all deposition temperatures with a continuous variation in spinel composition in between. The dependence of the film surface microstructure on the deposition temperature and the composition was mapped. Moreover, the band gap values, ranging from 2.41 eV for FeCo 2 O 4 to 2.74 eV for Fe 2 CoO 4 , show a continuous variation with the composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantitative Infrared-to-Terahertz Nanospectroscopy of Semiconductors

Semiconductor technology now employs few-nanometer features, necessitating tools probing electronic properties on the same length scale. While the concentration of free charge carriers is routinely measured, the scattering rate remains challenging to access at the nanoscale. Here, we present ultrabroadband (5–50 THz) synchrotron infrared nanospectroscopy as a quantitative metrology tool for semiconductors. This technique can determine both the charge carrier concentration and scattering rate with percent-level accuracy, and it is inherently capable of ∼10 nm spatial resolution. We study silicon with different doping levels and confirm the method’s accuracy by statistical analysis and comparison with established far-field infrared spectroscopy. Near-field measurements systematically reveal charge-carrier concentrations ∼30% lower than far-field values, consistent with increased surface sensitivity and surface depletion. Our work establishes synchrotron infrared nanospectroscopy as a precise tool for quantitative nanoscale semiconductor characterization and paves the way toward all-optical characterization of surface depletion effects.

36 MATERIALS SCIENCE↗

Cellulose Nanocrystals’ Role in Critical Mineral Beneficiation: Dual Aggregate-Dispersant Behavior Supports Environmentally Benign Nickel Processing

Environmentally unsustainable and toxic chemical flocculants and dispersants from nickel (Ni) processing contribute to industrial effluents that greatly impact biodiversity and aquatic life. Despite the industry’s efforts to reduce its ecological footprint—primarily due to the lack of commercially available biodegradable, environmentally benign, and non-toxic reagents—these reagents continue to harm natural ecosystems. Chemicals used during the processing operations often target a specific unit operation that negatively affects downstream operations. In this study, we discover the concentration-dependent behavior of cellulose nanocrystals (CNCs) as a dispersant and flocculant, avoiding the use of various harmful chemicals in the nickel processing stages. Electrophoretic, optical brightfield microscopy, and quartz crystal microbalance-dissipation studies detected charge neutralization behavior by renewable and biodegradable CNCs, which can greatly benefit Ni processing operations. Microflotation experiments demonstrated that CNCs enhanced Ni recovery from 62 to 77 wt.% and concentrate grade from 15 to 20 wt.%. Settling and turbidity studies demonstrated the dual flocculant-dispersant behavior of CNCs resulting from the alignment of CNC fibers along the octahedral brucite basal and amphoteric edge plane of serpentine. CNCs can be used as dispersants during froth flotation to improve Ni beneficiation and as post-processing flocculants for tailings management and dewatering, which is one of the major environmental and social concerns facing the mining and mineral processing industry. This study paves the way for CNCs to be used as flocculants and dispersants in a range of industries from healthcare to pharmaceuticals to semiconductor devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals

The realization of long-range ferromagnetic order in two-dimensional van der Waals crystals, combined with their rich electronic and optical properties, could lead to new magnetic, magnetoelectric and magneto-optic applications1,2,3,4. In two-dimensional systems, the long-range magnetic order is strongly suppressed by thermal fluctuations, according to the Mermin–Wagner theorem5; however, these thermal fluctuations can be counteracted by magnetic anisotropy. Previous efforts, based on defect and composition engineering6,7,8,9,10, or the proximity effect, introduced magnetic responses only locally or extrinsically. Here we report intrinsic long-range ferromagnetic order in pristine Cr2Ge2Te6 atomic layers, as revealed by scanning magneto-optic Kerr microscopy. In this magnetically soft, two-dimensional van der Waals ferromagnet, we achieve unprecedented control of the transition temperature (between ferromagnetic and paramagnetic states) using very small fields (smaller than 0.3 tesla). This result is in contrast to the insensitivity of the transition temperature to magnetic fields in the three-dimensional regime. We found that the small applied field leads to an effective anisotropy that is much greater than the near-zero magnetocrystalline anisotropy, opening up a large spin-wave excitation gap. We explain the observed phenomenon using renormalized spin-wave theory and conclude that the unusual field dependence of the transition temperature is a hallmark of soft, two-dimensional ferromagnetic van der Waals crystals. Cr2Ge2Te6 is a nearly ideal two-dimensional Heisenberg ferromagnet and so will be useful for studying fundamental spin behaviours, opening the door to exploring new applications such as ultra-compact spintronics.

Gong, Cheng↗

Long-range exciton transport and slow annihilation in two-dimensional hybrid perovskites

Two-dimensional hybrid organic-inorganic perovskites with strongly bound excitons and tunable structures are desirable for optoelectronic applications. Exciton transport and annihilation are two key processes in determining device efficiencies; however, a thorough understanding of these processes is hindered by that annihilation rates are often convoluted with exciton diffusion constants. Here we employ transient absorption microscopy to disentangle quantum-well-thickness-dependent exciton diffusion and annihilation in twodimensional perovskites, unraveling the key role of electron-hole interactions and dielectric screening. The exciton diffusion constant is found to increase with quantum-well thickness, ranging from 0.06 ± 0.03 to 0.34 ± 0.03 cm 2 s –1 , which leads to long-range exciton diffusion over hundreds of nanometers. The exciton annihilation rates are more than one order of magnitude lower than those found in the monolayers of transition metal dichalcogenides. The combination of long-range exciton transport and slow annihilation highlights the unique attributes of two-dimensional perovskites as an exciting class of optoelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microsecond fingerprint stimulated Raman spectroscopic imaging by ultrafast tuning and spatial-spectral learning

Label-free vibrational imaging by stimulated Raman scattering (SRS) provides unprecedented insight into real-time chemical distributions. Specifically, SRS in the fingerprint region (400–1800 cm -1 ) can resolve multiple chemicals in a complex bio-environment. However, due to the intrinsic weak Raman cross-sections and the lack of ultrafast spectral acquisition schemes with high spectral fidelity, SRS in the fingerprint region is not viable for studying living cells or large-scale tissue samples. Here, we report a fingerprint spectroscopic SRS platform that acquires a distortion-free SRS spectrum at 10 cm -1 spectral resolution within 20 µs using a polygon scanner. Meanwhile, we significantly improve the signal-to-noise ratio by employing a spatial-spectral residual learning network, reaching a level comparable to that with 100 times integration. Collectively, our system enables high-speed vibrational spectroscopic imaging of multiple biomolecules in samples ranging from a single live microbe to a tissue slice.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Pressure-induced structural phase transitions in CrSBr

There is growing interest in combining chemical complexity with external stimuli like pressure, field, and light for property control in van der Waals solids. This is because extreme conditions trigger the development of new states of matter and functionality. In this work, we bring together synchrotron-based infrared absorption, Raman scattering, and diamond anvil cell techniques with first-principles calculations of the lattice dynamics and energy landscape to reveal the series of structural phase transitions in CrSBr. By tracking how the phonons change under pressure, we uncover a remarkable chain of complex symmetry modifications, interlayer interactions, and chemical reactions. A group-subgroup analysis suggests that CrSBr undergoes an orthorhombic Pmmn → monoclinic P2/m transition at 7.6 GPa, and based upon a comparison with model oxychlorides like FeOCl and CrOCl, we propose that changes in the pendant halide groups drive the system to a P2 1 /m-like space group above 15.3 GPa. Compression above 20.2 GPa is irreversible, resulting in the formation of an entirely new compound that is metastable for months. This work opens the door to the use of pressure and possibly strain to control the properties of CrSBr.

Microscopy↗

On-demand nanoengineering of in-plane ferroelectric topologies

Hierarchical assemblies of ferroelectric nanodomains, so-called super-domains, can exhibit exotic morphologies that lead to distinct behaviours. Controlling these super-domains reliably is critical for realizing states with desired functional properties. Here we reveal the super-switching mechanism by using a biased atomic force microscopy tip, that is, the switching of the in-plane super-domains, of a model ferroelectric Pb 0.6 Sr 0.4 TiO 3 . We demonstrate that the writing process is dominated by a super-domain nucleation and stabilization process. A complex scanning-probe trajectory enables on-demand formation of intricate centre-divergent, centre-convergent and flux-closure polar structures. Correlative piezoresponse force microscopy and optical spectroscopy confirm the topological nature and tunability of the emergent structures. The precise and versatile nanolithography in a ferroic material and the stability of the generated structures, also validated by phase-field modelling, suggests potential for reliable multi-state nanodevice architectures and, thereby, an alternative route for the creation of tunable topological structures for applications in neuromorphic circuits.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

X-ray ptychographic and fluorescence microscopy of frozen-hydrated cells using continuous scanning

X-ray microscopy can be used to image whole, unsectioned cells in their native hydrated state. It complements the higher resolution of electron microscopy for submicrometer thick specimens, and the molecule-specific imaging capabilites of fluorescence light microscopy. We describe here the first use of fast, continuous x-ray scanning of frozen hydrated cells for simultaneous sub-20 nm resolution ptychographic transmission imaging with high contrast, and sub-100 nm resolution deconvolved x-ray fluorescence imaging of diffusible and bound ions at native concentrations, without the need to add specific labels. Here, by working with cells that have been rapidly frozen without the use of chemical fixatives, and imaging them under cryogenic conditions, we are able to obtain images with well preserved structural and chemical composition, and sufficient stability against radiation damage to allow for multiple images to be obtained with no observable change.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗