Genome-wide characterization of LBD transcription factors in switchgrass (Panicum virgatum L.) and the involvement of PvLBD12 in salt tolerance.

KEY MESSAGE: PvLBD12 enhanced the salt tolerance by increasing proline accumulation, improving K+ accumulation, and decreasing reactive oxygen species level in switchgrass. Abiotic stresses are the serious factors which limit plant development and productivity and restrict the agricultural economy. It is important, therefore, to understand the mechanism of abiotic tolerance in plants. Lateral organ boundaries domain (LBD) proteins as plant-specific transcription factors play important function in plant lateral organ development, plant regeneration, and abiotic stress. In our study, we identify 69 LBD members from switchgrass genome-wide sequences and classify them based on their homology with LBD proteins in Arabidopsis. RT-qPCR showed that PvLBD genes had different expression patterns under abiotic stress conditions, indicating that they play important roles in various stress. PvLBD12 was selected as a candidate gene for further functional analysis because it had the highest expression level under salt stress. Overexpression of PvLBD12 enhanced salt tolerance by altering a wide range of physiological responses (like increased proline accumulation, reduced malondialdehyde production, improved K+ accumulation, and reduced Na+ absorption) in switchgrass. Some stress response genes such as proline biosynthesis gene PvP5CS1, vacuolar Na+(K+)/H+ antiporter gene PvNHX1, two key ROS-scavenging enzyme genes PvCAT and PvSOD were all upregulated in PvLBD12 overexpression lines. Taken together, PvLBD12 plays a pivotal role in response to salt stress by increasing proline accumulation, improving K+ accumulation, reducing Na+ absorption, and decreasing reactive oxygen species level. It will be better to understand the potential biological functions of LBD genes in other plants.

Ultrahigh Temperature Lead-Free Film Capacitors via Strain and Dielectric Constant Double Gradient Design.

With the development of miniaturization, lightweight and integration of electronic devices, the demand for high-temperature dielectric capacitors is becoming urgent. Nevertheless, the breakdown strength and polarization are deteriorated at high temperatures due to the thermal energy assisting the electron transport and impeding the dipole alignment. Here, a structure of capacitor with double gradients of dielectric constant gradient and strain gradient is designed to achieve high breakdown strength, high working temperature, and high energy storage density simultaneously. It is found that the designed structure of BaHf0.17 Ti0.83 O3 /1mol% SiO2 doped BaZr0.35 Ti0.65 O3 /0.85BaTiO3 -0.15Bi(Mg0.5 Zr0.5 )O3 exhibits excellent energy storage performance. The energy storage density of 127.3 J cm-3 with an energy storage efficiency of 79.6% is realized in the up-sequence multilayer with period N = 2 at room temperature. Moreover, when the working temperature varies from -100 to 200 °C, the energy storage density of the N = 4 capacitor keeps stably at 84.62 J cm-3 with an energy storage efficiency 78.42% at 6.86 MV cm-1 . All these properties promise great potential applications of the designed multilayer capacitors with the double gradients in harsh environments, and the design principle can be applicable to other systems to boost working temperature.

Changing the Phosphorus Allotrope from a Square Columnar Structure to a Planar Zigzag Nanoribbon by Increasing the Diameter of Carbon Nanotube Nanoreactors.

Elemental phosphorus nanostructures are notorious for a large number of allotropes, which limits their usefulness as semiconductors. To limit this structural diversity, we synthesize selectively quasi-1D phosphorus nanostructures inside carbon nanotubes (CNTs) that act both as stable templates and nanoreactors. Whereas zigzag phosphorus nanoribbons form preferably in CNTs with an inner diameter exceeding 1.4 nm, a previously unknown square columnar structure of phosphorus is observed to form inside narrower nanotubes. Our findings are supported by electron microscopy and Raman spectroscopy observations as well as ab initio density functional theory calculations. Our computational results suggest that square columnar structures form preferably in CNTs with an inner diameter around 1.0 nm, whereas black phosphorus nanoribbons form preferably inside CNTs with a 4.1 nm inner diameter, with zigzag nanoribbons energetically favored over armchair nanoribbons. Our theoretical predictions agree with the experimental findings.

De novo transcriptome assembly and population genetic analyses of an important coastal shrub, Apocynum venetum L.

BACKGROUND: Apocynum venetum L. is an important medicinal plant that is mainly distributed in the coastal areas and northwest of China. In addition to its high medical and economic value, its adaptation to saline-alkali and coastal saline lands makes A. venetum an ideal candidate for use in vegetation restoration. To date, the study of A. venetum has been limited in the northwest region of China, little attention has been paid to the genetic diversity and population structure of A. venetum populations in the coastal region. Here, we performed transcriptome sequencing of total RNA from A. venetum leaves and developed efficient expressed sequence tag-simple sequence repeat (EST-SSR) markers for analyzing the genetic diversity and population structure of A. venetum in the coastal region. RESULTS: A total of 86,890 unigenes were generated after de novo assembly, and 68,751 of which were successfully annotated by searching against seven protein databases. Furthermore, 14,072 EST-SSR loci were detected and 10,243 primer pairs were successfully designed from these loci. One hundred primer pairs were randomly selected and synthesized, twelve primer pairs were identified as highly polymorphic and further used for population genetic analysis. Population genetic analyses showed that A. venetum exhibited low level of genetic diversity (mean alleles per locus, NA = 3.3; mean expected heterozygosity, HE = 0.342) and moderate level of genetic differentiation among the populations (genetic differentiation index, FST = 0.032-0.220) in the coastal region. Although the contemporary (mean mc = 0.056) and historical (mean mh = 0.106) migration rates among the six A. venetum populations were moderate, a decreasing trend over the last few generations was detected. Bayesian structure analysis clustered six populations into two major groups, and genetic bottlenecks were found to have occurred in two populations (QG, BH). CONCLUSIONS: Using novel EST-SSR markers, we evaluated the genetic variation of A. venetum in the coastal region and determined conservation priorities based on these findings. The large dataset of unigenes and SSRs identified in our study, combining samples from a broader range, will support further research on the conservation and evolution of this important coastal plant and its related species.

Local crystallographic shear structures in a[201] extended mixed dislocations of SrTiO3 unraveled by atomic-scale imaging using transmission electron microscopy and spectroscopy.

Recently, extended mixed dislocations were observed at a [001]/(100) low-angle tilt grain boundary of a SrTiO3 bicrystal because of a slight twist between the two crystal parts. The b = a[201]/(100) mixed dislocations at the grain boundary dissociate into three dislocations with Burgers vector b of a/2[101], a[100], and a/2[101], respectively. A structure model has been proposed in particular for the dislocation cores of the two partials with b = a/2[101] based on the high-angle annular dark-field (HAADF) images acquired by scanning transmission electron microscopy (STEM). However, the details of the atomic structure and the chemical composition of the dislocation cores remain unexplored, especially for the b = a[100] dislocation that is evidently disassociated into two b = a/2[101] partial dislocations. In this work, we study the further atomic details of the extended mixed dislocations, in particular the local chemistry, in a SrTiO3 bicrystal using STEM, electron energy loss spectroscopy (EELS), and energy dispersive X-ray (EDX) spectroscopy techniques. By these atomic-scale imaging techniques, we reveal a unique feature for the atomic structure of the b = a[201]/(100) extended mixed dislocation, which we named as local crystallographic shear (LCS) structures. In addition, we identify a rock salt FCC-type TiOx (x = 0.66-1.24) phase at the locations of the extended mixed dislocations. In contrast to the insulating TiO2 phases, the TiOx phase is known to exhibit very low electrical resistivity of only several µΩ cm. In this regard, the extended mixed dislocations of SrTiO3 comprising the FCC TiOx phase may function as the conducting filament in resistive switching processes by completion and disruption of the TiOx phase along the dislocation cores through electrically stimulated redox reactions.

Topological Defects with Distinct Dipole Configurations in PbTiO_{3}/SrTiO_{3} Multilayer Films.

Distinct and novel features of nanometric electric topological defects, including dipole waves and dipole disclinations, are presently revealed in the PbTiO_{3} layers of PbTiO_{3}/SrTiO_{3} multilayer films by means of quantitative high-resolution scanning transmission electron microscopy. These original dipole configurations are confirmed and explained by atomistic simulations and have the potential to act as functional elements in future electronics.

Assembly of Ring-Shaped Phosphorus within Carbon Nanotube Nanoreactors.

A phosphorus allotrope that has not been observed so far, ring-shaped phosphorus consisting of alternate P8 and P2 structural units, has been assembled inside multi-walled carbon nanotube nanoreactors with inner diameters of 5-8 nm by a chemical vapor transport and reaction of red phosphorus at 500 °C. The ring-shaped nanostructures with surrounding graphene walls are stable under ambient conditions. The nanostructures were characterized by high-resolution transmission electron microscopy, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, Raman scattering, attenuated total reflectance Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy.

Functional conservation and divergence of Miscanthus lutarioriparius GT43 gene family in xylan biosynthesis.

BACKGROUND: Xylan is the most abundant un-cellulosic polysaccharides of plant cell walls. Much progress in xylan biosynthesis has been gained in the model plant species Arabidopsis. Two homologous pairs Irregular Xylem 9 (IRX9)/9L and IRX14/14L from glycosyltransferase (GT) family 43 have been proved to play crucial roles in xylan backbone biosynthesis. However, xylan biosynthesis in grass such as Miscanthus remains poorly understood. RESULTS: We characterized seven GT43 members in M. lutarioriparius, a promising bioenergy crop. Quantitative real-time RT-PCR (qRT-PCR) analysis revealed that the expression of MlGT43 genes was ubiquitously detected in the tissues examined. In-situ hybridization demonstrated that MlGT43A-B and MlGT43F-G were specifically expressed in sclerenchyma, while MlGT43C-E were expressed in both sclerenchyma and parenchyma. All seven MlGT43 proteins were localized to Golgi apparatus. Overexpression of MlGT43A-E but not MlGT43F and MlGT43G in Arabidopsis irx9 fully or partially rescued the mutant defects, including morphological changes, collapsed xylem and increased xylan contents, whereas overexpression of MlGT43F and MlGT43G but not MlGT43A-E complemented the defects of irx14, indicating that MlGT43A-E are functional orthologues of IRX9, while MlGT43F and MlGT43G are functional orthologues of IRX14. However, overexpression of all seven MlGT43 genes could not rescue the mucilage defects of irx14 seeds. Furthermore, transient transactivation analyses of MlGT43A-E reporters demonstrated that MlGT43A and MlGT43B but not MlGT43C-E were differentially activated by MlSND1, MlMYB46 or MlVND7. CONCLUSION: The results demonstrated that all seven MlGT43s are functionally conserved in xylan biosynthesis during secondary cell wall formation but diversify in seed coat mucilage xylan biosynthesis. The results obtained provide deeper insight into xylan biosynthesis in grass, which lay the foundation for genetic modification of grass cell wall components and structure to better suit for next-generation biofuel production.

Responses of diazotrophic network structure and community diversity to alfalfa-maize intercropping are soil property-dependent.

Introduction: Intercropping and soil properties both affect soil diazotrophic communities. However, the specific effects that alfalfa-maize intercropping has on diazotrophic networks and community diversity under different soil properties remain unclear. Methods: In this study, we investigated the soil diazotrophic communities of two crop systems, alfalfa monoculture (AA) and alfalfa-maize intercropping (A/M), in two sites with similar climates but different soil properties (poor vs. average). Results and discussion: The diazotrophic network complexity and community diversity were higher at the site with poor soil than at the site with average soil (p < 0.05). Community structure also varied significantly between the sites with poor and average soil (p < 0.05). This divergence was mainly due to the differences in soil nitrogen, phosphorus, and organic carbon contents between the two sites. At the site with poor soil, the A/M system had lower diazotrophic diversity, lower network complexity and greater competition between diazotrophs than the AA system (p < 0.05) because intercropping intensified the soil phosphorus limitation under poor soil conditions. However, in the average soil, it was the A/M system that had an altered diazotrophic structure, with an increased abundance of 11 bacterial genera and a decreased abundance of three bacterial genera (p < 0.05). Conclusion: Our results indicated that the effects of alfalfa-maize intercropping on diazotrophic communities were soil property-dependent.

Transcriptomic analysis of ncRNAs and mRNAs interactions during drought stress in switchgrass.

Switchgrass (Panicum virgatum L.) plays a pivotal role as a bioenergy feedstock in the production of cellulosic ethanol and contributes significantly to enhancing ecological grasslands and soil quality. The utilization of non-coding RNAs (ncRNAs) has gained momentum in deciphering the intricate genetic responses to abiotic stress in various plant species. Nevertheless, the current research landscape lacks a comprehensive exploration of the responses of diverse ncRNAs, including long non-coding RNAs (lncRNAs), circular RNAs (circRNAs), and microRNAs (miRNAs), to drought stress in switchgrass. In this study, we employed whole transcriptome sequencing to comprehensively characterize the expression profiles of both mRNA and ncRNAs during episodes of drought stress in switchgrass. Our analysis identified a total of 12,511 mRNAs, 59 miRNAs, 38 circRNAs, and 368 lncRNAs that exhibited significant differential expression between normal and drought-treated switchgrass leaves. Notably, the majority of up-regulated mRNAs displayed pronounced enrichment within the starch and sucrose metabolism pathway, as validated through KEGG analysis. Co-expression analysis illuminated that differentially expressed (DE) lncRNAs conceivably regulated 1308 protein-coding genes in trans and 7110 protein-coding genes in cis. Furthermore, both cis- and trans-target mRNAs of DE lncRNAs exhibited enrichment in four common KEGG pathways. The intricate interplay between lncRNAs and circRNAs with miRNAs via miRNA response elements was explored within the competitive endogenous RNA (ceRNA) network framework. As a result, we constructed elaborate regulatory networks, including lncRNA-novel_miRNA480-mRNA, lncRNA-novel_miRNA304-mRNA, lncRNA/circRNA-novel_miRNA122-PvSS4, and lncRNA/circRNA-novel_miRNA14-PvSS4, and subsequently validated the functionality of the target gene, starch synthase 4 (PvSS4). Furthermore, through the overexpression of PvSS4, we ascertained its capacity to enhance drought tolerance in yeast. However, it is noteworthy that PvSS4 did not exhibit any discernible impact under salt stress conditions. These findings, as presented herein, not only contribute substantively to our understanding of ceRNA networks but also offer a basis for further investigations into their potential functions in response to drought stress in switchgrass.

Metadielectrics for high-temperature energy storage capacitors.

Dielectric capacitors are highly desired for electronic systems owing to their high-power density and ultrafast charge/discharge capability. However, the current dielectric capacitors suffer severely from the thermal instabilities, with sharp deterioration of energy storage performance at elevated temperatures. Here, guided by phase-field simulations, we conceived and fabricated the self-assembled metadielectric nanostructure with HfO2 as second-phase in BaHf0.17Ti0.83O3 relaxor ferroelectric matrix. The metadielectric structure can not only effectively increase breakdown strength, but also broaden the working temperature to 400 oC due to the enhanced relaxation behavior and substantially reduced conduction loss. The energy storage density of the metadielectric film capacitors can achieve to 85 joules per cubic centimeter with energy efficiency exceeding 81% in the temperature range from 25 °C to 400 °C. This work shows the fabrication of capacitors with potential applications in high-temperature electric power systems and provides a strategy for designing advanced electrostatic capacitors through a metadielectric strategy.

Atomic-scale measurement of structure and chemistry of a single-unit-cell layer of LaAlO3 embedded in SrTiO3.

A single layer of LaAlO3 with a nominal thickness of one unit cell, which is sandwiched between a SrTiO3 substrate and a SrTiO3 capping layer, is quantitatively investigated by high-resolution transmission electron microscopy. By the use of an aberration-corrected electron microscope and by employing sophisticated numerical image simulation procedures, significant progress is made in two aspects. First, the structural as well as the chemical features of the interface are determined simultaneously on an atomic scale from the same specimen area. Second, the evaluation of the structural and chemical data is carried out in a fully quantitative way on the basis of the absolute image contrast, which has not been achieved so far in materials science investigations using high-resolution electron microscopy. Considering the strong influence of even subtle structural details on the electronic properties of interfaces in oxide materials, a fully quantitative interface analysis, which makes positional data available with picometer precision together with the related chemical information, can contribute to a better understanding of the functionality of such interfaces.

Improved Leakage Behavior at High Temperature via Engineering of Ferroelectric Sandwich Structures.

The leakage behavior of ferroelectric film has an important effect on energy storage characteristics. Understanding and controlling the leakage mechanism of ferroelectric film at different temperatures can effectively improve its wide-temperature storage performance. Here, the structures of a 1 mol% SiO2-doped BaZr0.35Ti0.65O3 (BZTS) layer sandwiched between two undoped BaZr0.35Ti0.65O3 (BZT35) layers was demonstrated, and the leakage mechanism was analyzed compared with BZT35 and BZTS single-layer film. It was found that interface-limited conduction of Schottky (S) emission and the Fowler-Nordheim (F-N) tunneling existing in BZT35 and BZTS films under high temperature and a high electric field are the main source of the increase of leakage current and the decrease of energy storage efficiency at high temperature. Only an ohmic conductive mechanism exists in the whole temperature range of BZT35/BZTS/BZT35(1:1:1) sandwich structure films, indicating that sandwich multilayer films can effectively simulate the occurrence of interface-limited conductive mechanisms and mention the energy storage characteristics under high temperature.

Metavalent Bonding in Layered Phase-Change Memory Materials.

Metavalent bonding (MVB) is characterized by the competition between electron delocalization as in metallic bonding and electron localization as in covalent or ionic bonding, serving as an essential ingredient in phase-change materials for advanced memory applications. The crystalline phase-change materials exhibits MVB, which stems from the highly aligned p orbitals and results in large dielectric constants. Breaking the alignment of these chemical bonds leads to a drastic reduction in dielectric constants. In this work, it is clarified how MVB develops across the so-called van der Waals-like gaps in layered Sb2 Te3 and Ge-Sb-Te alloys, where coupling of p orbitals is significantly reduced. A type of extended defect involving such gaps in thin films of trigonal Sb2 Te3 is identified by atomic imaging experiments and ab initio simulations. It is shown that this defect has an impact on the structural and optical properties, which is consistent with the presence of non-negligible electron sharing in the gaps. Furthermore, the degree of MVB across the gaps is tailored by applying uniaxial strain, which results in a large variation of dielectric function and reflectivity in the trigonal phase. At last, design strategies are provided for applications utilizing the trigonal phase.

Beijing Pinggu Childhood Eye Study: The Baseline Refractive Characteristics in 6- to 12-Year-Old Chinese Primary School Students.

Purpose: To report the design and baseline data of a 3-year cohort study in Beijing Pinggu District primary school students in China after COVID-19. Methods: Noncycloplegic and cycloplegic spherical equivalent refraction (SER) were measured, ocular biometry, including the axial length (AL), anterior chamber depth (ACD) and corneal power (CP), were collected before cycloplegia. Corneal radius (CR), AL-to-CR ratio, and lens power (LP) were calculated. Results: Among the 4,806 (89.1%) eligible students (51.5% male), the prevalence of emmetropia, myopia, mild hyperopia, and mild-to-high hyperopia was 12.8, 30.8, 53.0, and 3.3% after cycloplegia, respectively. Myopia increased from 2.5% in 6- to 71.6% in 12-year-old students, with 9- and 10-year-olds showing the most prominent increases. The median of cycloplegic SER was 0.50 (IQR = 1.63), and the noncycloplegic SER was -0.38 D (IQR = 1.50), which is more negative than the cycloplegic refraction. The mean AL increased with age, from 22.46 ± 0.70 mm to 24.26 ± 1.07 mm. The ACD increased from 3.38 ± 0.28 mm to 3.70 ± 0.30 mm, and the AL-to-CR ratio increased from 2.91 ± 0.08 to 3.12 ± 0.13 between 6- and 12-year-old students. AL, CR and LP explained the SER variance with R2 of 86.4% after adjusting the age and gender. Conclusions and Relevance: The myopia prevalence since emergence of COVID-19 rapidly increased from 6- to 12-year primary school Chinese children, especially after 7 years of age. The non-cycloplegia SER overestimated the prevalence of myopia, and the cycloplegic SER is a more accurate and reliable method to assess the prevalence of refractive status.

Designing Conductive-Bridge Phase-Change Memory to Enable Ultralow Programming Power.

Phase-change material (PCM) devices are one of the most mature nonvolatile memories. However, their high power consumption remains a bottleneck problem limiting the data storage density. One may drastically reduce the programming power by patterning the PCM volume down to nanometer scale, but that route incurs a stiff penalty from the tremendous cost associated with the complex nanofabrication protocols required. Instead, here a materials solution to resolve this dilemma is offered. The authors work with memory cells of conventional dimensions, but design/exploit a PCM alloy that decomposes into a heterogeneous network of nanoscale crystalline domains intermixed with amorphous ones. The idea is to confine the subsequent phase-change switching in the interface region of the crystalline nanodomain with its amorphous surrounding, forming/breaking "nano-bridges" that link up the crystalline domains into a conductive path. This conductive-bridge switching mechanism thus only involves nanometer-scale volume in programming, despite of the large areas in contact with the electrodes. The pore-like devices based on spontaneously phase-separated Ge13 Sb71 O16 alloy enable a record-low programming energy, down to a few tens of femtojoule. The new PCM/fabrication is fully compatible with the current 3D integration technology, adding no expenses or difficulty in processing.

Ferroelectric phase-transition frustration near a tricritical composition point.

Phase transition describes a mutational behavior of matter states at a critical transition temperature or external field. Despite the phase-transition orders are well sorted by classic thermodynamic theory, ambiguous situations interposed between the first- and second-order transitions were exposed one after another. Here, we report discovery of phase-transition frustration near a tricritical composition point in ferroelectric Pb(Zr1-xTix)O3. Our multi-scale transmission electron microscopy characterization reveals a number of geometrically frustrated microstructure features such as self-assembled hierarchical domain structure, degeneracy of mesoscale domain tetragonality and decoupled polarization-strain relationship. Associated with deviation from the classic mean-field theory, dielectric critical exponent anomalies and temperature dependent birefringence data unveil that the frustrated transition order stems from intricate competition of short-range polar orders and their decoupling to long-range lattice deformation. With supports from effective Hamiltonian Monte Carlo simulations, our findings point out a potentially universal mechanism to comprehend the abnormal critical phenomena occurring in phase-transition materials.

Enhanced Energy Storage Performance of Lead-Free Capacitors in an Ultrawide Temperature Range via Engineering Paraferroelectric and Relaxor Ferroelectric Multilayer Films.

Industry has been seeking a thin-film capacitor that can work at high temperature in a harsh environment, where cooling systems are not desired. Up to now, the working temperature of the thin-film capacitor is still limited up to 200 °C. Herein, we design a multilayer structure with layers of paraferroelectric (Ba0.3Sr0.7TiO3, BST) and relaxor ferroelectric (0.85BaTiO3-0.15Bi(Mg0.5Zr0.5)O3, BT-BMZ) to realize optimum properties with a flat platform of dielectric constant and high breakdown strength for excellent energy storage performance at high temperature. Through optimizing the multilayer structure, a highly stable relaxor ferroelectric state is obtained for the BST/BT-BMZ multilayer thin-film capacitor with a total thickness of 230 nm, a period number N = 8, and a layer thickness ratio of BST/BT-BMZ = 3/7. The optimized multilayer film shows significantly improved energy storage density (up to 30.64 J/cm3) and energy storage efficiency (over 70.93%) in an ultrawide temperature range from room temperature to 250 °C. Moreover, the multilayer system also exhibits excellent thermal stability in such an ultrawide temperature range with a change of 5.15 and 12.75% for the recoverable energy density and energy storage efficiency, respectively. Our results demonstrate that the designed thin-film capacitor is promising for the application in a harsh environment and open a way to tailor a thin-film capacitor toward higher working temperature with enhanced energy storage performance.

An Unconventional Transient Phase with Cycloidal Order of Polarization in Energy-Storage Antiferroelectric PbZrO3.

Antiferroelectric-based dielectric capacitors are receiving tremendous attention for their outstanding energy-storage performance and extraordinary flexibility in collecting pulsed powers. Nevertheless, the in situ atomic-scale structural-evolution pathway, inherently coupling to the energy storage process, has not been elucidated for the ultimate mechanistic understanding so far. Here, time- and atomic-resolution structural phase evolution in antiferroelectric PbZrO3 during storage of energy from the electron-beam illumination is reported. By employing state-of-the-art negative-spherical-aberration imaging technique, the quantitative transmission electron microscopy study presented herein clarifies that the hierarchical evolution of polar oxygen octahedra associated with the unit-cell volume change and polarization rotation accounts for the stepwise antiferroelectric-to-ferroelectric phase transition. In particular, an unconventional ferroelectric category-the ferrodistortive phase characteristic of a unique cycloidal polarization order-is established during the dynamic structure investigation. Through clarifying the atomic-scale phase transformation pathway, findings of this work unveil a new territory to explore novel ferrodistortive phases in energy-storage materials with the nonpolar-to-polar phase transitions.

Sub-Angstrom Characterization of the Structural Origin for High In-Plane Anisotropy in 2D GeS2.

Materials with layered crystal structures and high in-plane anisotropy, such as black phosphorus, present unique properties and thus promise for applications in electronic and photonic devices. Recently, the layered structures of GeS2 and GeSe2 were utilized for high-performance polarization-sensitive photodetection in the short wavelength region due to their high in-plane optical anisotropy and wide band gap. The highly complex, low-symmetric (monoclinic) crystal structures are at the origin of the high in-plane optical anisotropy, but the structural nature of the corresponding nanostructures remains to be fully understood. Here, we present an atomic-scale characterization of monoclinic GeS2 nanostructures and quantify the in-plane structural anisotropy at the sub-angstrom level in real space by Cs-corrected scanning transmission electron microscopy. We elucidate the origin of this high in-plane anisotropy in terms of ordered and disordered arrangement of [GeS4] tetrahedra in GeS2 monolayers, through density functional theory (DFT) calculations and orbital-based bonding analyses. We also demonstrate high in-plane mechanical, electronic, and optical anisotropies in monolayer GeS2 and envision phase transitions under uniaxial strain that could potentially be exploited for nonvolatile memory applications.