Xuanhao Wu, Mengmeng Niu, Xin Tian, Xiaoyan Peng, Pio John S. Buenconsej, Xu Wu, Yeliang Wang, Wei Ji, Yi Li, Jingsi Qiao,Jifang Tao, Mingming Zhang, Song Xiaof and Hongye Yuan
Abstract:
Developing sensitive metal–organic framework (MOF) systems to overcome the ubiquitous trade-off between porosity and conductivity remains a formidable yet sought-after endeavor. This pursuit is of great significance for the development of MOF-based chemiresistive sensors with enhanced sensitivity and selectivity. Herein, we present an innovative template assisted strategy that utilizes the two-dimensional properties and good conductivity of MXene nanosheets, as well as lattice matching between MXene (Nb2C) and selected Ni3(HITP)2, to achieve controllable self-assembly of Ni3(HITP)2 on MXene sheets. This results in Ni3(HITP)2/MXene (HITP: 2,3,6,7,10,11-hexaaminotriphenylene) heterostructures with considerable conductivity, porosity, and solution processability. The powder and film electrical conductivity are 4.8 × 103 and 5.3 × 105 S m−1, respectively, and the BET specific surface area can reach 797.8 m2 g−1. It is worth noting that excellent solution processability helps to prepare large-area films (23 cm × 9 cm) with good uniformity. Gas sensors based on Ni3(HITP)2/MXene heterostructures exhibit high sensitivity (LOD ∼ 5 ppb) and selectivity towards ultratrace ethanol at room temperature, setting a new benchmark. Such sensing behavior stems from the strong coupling of Ni3(HITP)2/MXene heterostructures and their enhanced interaction with ethanol, evidenced by experimental results and theoretical calculations. Real-time respiratory sensing assessments underscore their practicality in healthcare monitoring. This straightforward approach simplifies the integration of MOF-related materials on miniaturized devices with outstanding performance.
Hafnia-based ferroelectric materials, like Hf0.5Zr0.5O2 (HZO), have received tremendous attention owing to their potentials for building ultra-thin ferroelectric devices. The orthorhombic(O)-phase of HZO is ferroelectric but metastable in its bulk form under ambient conditions, which poses a considerable challenge to maintaining the operation performance of HZO-based ferroelectric devices. Here, we theoretically addressed this issue that provides parameter spaces for stabilizing the O-phase of HZO thin-films under various conditions. Three mechanisms were found to be capable of lowering the relative energy of the O-phase, namely, more significant surface-bulk portion of (111) surfaces, compressive caxis strain, and positive electric fields. Considering these mechanisms, we plotted two ternary phase diagrams for HZO thin-films where the strain was applied along the in-plane uniaxial and biaxial, respectively. These diagrams indicate the O-phase could be stabilized by solely shrinking the film-thickness below 12.26 nm, ascribed to its lower surface energies. All these results shed considerable light on designing more robust and higher-performance ferroelectric devices.
Nanshu Liu, Cong Wang, Changlin Yan, Changsong Xu, Jun Hu, Yanning Zhang, and Wei Ji
Abstract:
A recent experiment reported type-II multiferroicity in monolayer (ML) NiI2 based on a presumed spiral magnetic configuration (Spiral-B), which is, as we found here, under debate in the ML limit. Freestanding ML NiI2 breaks its C3 symmetry, as it prefers a striped antiferromagnetic order (AABB-AFM) along with an intralayer antiferroelectric (AFE) order. However, substrate confinement may preserve the C3 symmetry and/or apply tensile strain to the ML. This leads to another spiral magnetic order (SpiralIVX), while 2L shows a different order (SpiralVX) and Spiral-B dominates in thicker layers. Thus, three multiferroic phases, namely, SpiralB+FE, Spiral-IVX +FE, Spiral-VX+FE, and an anti-multiferroic AABB-AFM+AFE one, show layer-thickness-dependent and geometry-dependent dominance, ascribed to competitions among thickness-dependent Kitaev, biquadratic, and Heisenberg spin–exchange interactions and single-ion magnetic anisotropy. Our theoretical results clarify the debate on the multiferroicity of ML NiI2 and shed light on the role of layer-stacking-induced changes in noncollinear spin–exchange interactions and magnetic anisotropy in thickness-dependent magnetism.
The intrinsic superlattice magnetic topological insulators of MnBi2Te4(Bi2Te3)𝑛 (𝑛=0,1,2…) provides a promising material platform for the realization of diverse exotic topological quantum states, such as quantum anomalous Hall effect and axion-insulator state. All these quantum states are sensitively dependent on the complex interplay and intertwinement of their band topology, magnetism, and defective structural details. Here, we report a comprehensive real-space investigation on the magnetic ordering states of MnBi2Te4(Bi2Te3)𝑛 using cryogenic magnetic force microscopy. The MnBi2Te4(Bi2Te3)𝑛 crystals exhibit a distinctive magnetic evolution from A-type antiferromagnetic to ferromagnetic states via the increased Bi2Te3 intercalation layers. The magnetic field- and temperature-dependent phase evolution behaviors of MnBi6Te10 and MnBi8Te13 are comparatively investigated to obtain the complete 𝐻−𝑇 phase diagrams. The combination impact of the intrinsic and defect-mediated interlayer coupling on their magnetic states were further discussed. Our results pave a possible way to realize more exotic quantum states via the tunable magnetic configurations in the artificial-stacking MnBi2Te4(Bi2Te3)𝑛 multilayers.
Deping Guo (郭的坪)#, Cong Wang (王聪)#, Lvjin Wang (王侣锦), Yunhao Lu (陆赟豪), Hua Wu (吴骅), Yanning Zhang (张妍宁), and Wei Ji (季威)*
Abstract:
Two-dimensional (2D) van der Waals magnetic materials have promising and versatile electronic and magnetic properties in the 2D limit, indicating a considerable potential to advance spintronic applications. Theoretical predictions thus far have not ascertained whether monolayer VCl3 is a ferromagnetic (FM) or anti-FM monolayer; this also remains to be experimentally verified. We theoretically investigate the influence of potential factors, including 𝐶3 symmetry breaking, orbital ordering, epitaxial strain, and charge doping, on the magnetic ground state. Utilizing first-principles calculations, we predict a collinear type-III FM ground state in monolayer VCl3 with a broken 𝐶3 symmetry, wherein only the former two of three 𝑡2g orbitals (𝑎1g, 𝑒 𝜋 g2 and 𝑒 𝜋 g1) are occupied. The atomic layer thickness and bond angles of monolayer VCl3 undergo abrupt changes driven by an orbital ordering switch, resulting in concomitant structural and magnetic phase transitions. Introducing doping to the underlying Cl atoms of monolayer VCl3 without 𝐶3 symmetry simultaneously induces in- and out-of-plane polarizations. This can achieve a multiferroic phase transition if combined with the discovered adjustments of magnetic ground state and polarization magnitude under strain. The establishment of an orbital-ordering driven regulatory mechanism can facilitate deeper exploration and comprehension of magnetic properties of strongly correlated systems in monolayer VCl3.
Boyu Fu#; Yurou Guan#; Wei Yuan#; Jianqun Geng#; Zhenliang Hao#; Zilin Ruan; Shijie Sun ; Yong Zhang; Wei Xiong; Lei Gao*; Yulan Chen*; Wei Ji*; Jianchen Lu*; Jinming Cai*
Abstract:
Tert-butyl functional groups can modulate the self-assembly behavior of organic molecules on surfaces. However, the precise construction of supramolecular architectures through their controlled thermal removal remains a challenge. Herein, we precisely controlled the removal amount of tert-butyl groups in tetraazaperopyrene derivatives by stepwise annealing on Ag(111). The evolution of 4tBu-TAPP supramolecular self-assembly from the grid-like structure composed of 3tBu-TAPP through the honeycomb network formed by 2tBu-TAPP to the one-dimensional chain co-assembled by tBu-TAPP and TAPP was successfully realized. This series of supramolecular nanostructures were directly visualized by high resolution scanning tunneling microscopy. Tip manipulation and density functional theory calculations show that the formation of honeycomb network structure can be attributed to the van der Waals interactions, N–Ag–N coordination bonds, and weak C–H⋯N hydrogen bonds. Further addition of two tert-butyl groups (6tBu-TAPP) leads to a completely different assembly evolution, due to the fact that the additional tert-butyl groups affect the molecular adsorption behavior and ultimately induce desorption. This work can possibly be exploited in constructing stable and long-range ordered nanostructures in surface-assisted systems, which can also promote the development of nanostructures in functional molecular devices.
