The newly discovered 2D magnetic materials provide new opportunities for basic physics and device applications. However, their low Curie temperature (TC) is a common weakness. In this paper, by combining magnetic Hamiltonian, Wannier functions and first-principle calculations, we systematically study the magnetic properties of monolayer CrI3 functionalized by halogen. The magnetic exchange coupling (EX) and magnetic anisotropy (MA) are found to increase significantly by X (X=F, Cl and Br) atom adsorption, and increase along with the coverage of X atom. In the frame work of superexchange theory, the enhanced EX can be ascribed to the reduced energy difference and increased hopping strength between Cr d and I p orbitals, due to the states of I ligand are engineered by X adatom. Besides, the X adatom may provide additional ferromagnetic superexchange channel. Finally, the CrI3 that one side is fully adsorbed by F atoms is found to be a room temperature ferromagnetic semiconductor with TC=650 K. Our results not only give an insightful understanding for the enhancement of ferromagnetism of CrI3 by atom adsorption, but also propose a promising way to improve the ferromagnetism of 2D magnetic materials.
Band gap tuning and dielectric properties of small organic ligands adsorbed on tin monolayers (stanene) have been investigated using first-principles calculations. Charge density analysis using density-functional theory shows that the ligands are chemisorbed on stanene and some of the groups can open a band gap in the originally metallic statene. Furthermore many-body GW calculations demonstrate that the dielectric properties of bare and ligand adsorbed stanene have a large anisotropy. Our findings of a finite gap opens a path for rational theoretical design of functionalized two-dimensional s…
Functionalization of photocatalytic metal oxide nanoparticles of TiO2, ZnO, WO3 and CuO with amine-terminated (oleylamine) and thiol-terminated (1-dodecanethiol) alkyl chained ligands was studied under ambient conditions. A high selectivity was observed in the binding specificity of a ligand towards nanoparticles of these different oxides. It was observed that oleylamine binds stably to only TiO2 and WO3, while 1-dodecanethiol binds stably only to ZnO and CuO. Similarly, polar to non-polar solvent phase transfer of TiO2 and WO3 nanoparticles could be achieved by using oleylamine, but not by 1-…
We investigate near-Fermi-energy (EF) element-specific electronic and spin states of ferromagnetic van der Waals (vdW) metal Fe5GeTe2. The soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) measurement provides spectroscopic evidence of localized Fe 3d band. We also find prominent hybridization between the localized Fe 3d band and the delocalized Ge/Te p bands. This picture is strongly supported from direct observation of the remarkable spin polarization of the ligand p bands near EF, using x-ray magnetic circular dichroism (XMCD) measurements. The strength of XMCD signal from lig…
We address the effect of functionalization on the electronic and magnetic properties of magnetite surface as an indicator of the same properties in nanoparticles too big for a direct ab-initio approach. Using well-established methods and references (namely LDA+U on magnetite surfaces) we could verify the validity of our approach, and using two typical ligands, dopamine and citrate, namely pi and sigma electron donors, we could predict that those ligands would induce a different change in the electronic properties of the systems, but in both cases an enhancement of magnetization.
(Ga,Fe)Sb is a promising ferromagnetic semiconductor for practical spintronic device applications because its Curie temperature ($T_{\rm C}$) is above room temperature. However, the origin of ferromagnetism with high $T_{\rm C}$ remains to be elucidated. Here, we use soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) to investigate the valence-band (VB) structure of (Ga$_{0.95}$,Fe$_{0.05}$)Sb including the Fe-3$d$ impurity band (IB), to unveil the mechanism of ferromagnetism in (Ga,Fe)Sb. We find that the VB dispersion in (Ga$_{0.95}$,Fe$_{0.05}$)Sb observed by SX-ARPES is simila…
Due to the predominantly surface character of graphene, it is highly suitable for functionalization with external atoms and/or molecules leading to a plethora of new and interesting phenomena. Here we show ferromagnetic properties of hydrogen-functionalized epitaxial graphene on SiC. Ferromagnetism in such a material is not directly evident as it is inherently composed of only non-magnetic constituents. Our results nevertheless show strong ferromagnetism, which cannot be explained by simple magnetic impurities. The ferromagnetism is unique to hydrogenated epitaxial graphene on SiC, where inter…
We show that the decomposition of caesium lead halide perovskite nanocrystals under continuous X-ray illumination depends on the surface ligand. For oleic acid/oleylamine, we observe a fast decay accompanied by the formation of elemental lead and halogen. Upon surface functionalization with a metal porphyrin derivate, the decay is markedly slower and involves the disproportionation of lead to Pb0 and Pb3+. In both cases, the decomposition is preceded by a contraction of the atomic lattice, which appears to initiate the decay. We find that the metal porphyrin derivative induces a strong surface…
Microscopic origin of the ferromagnetic (FM) exchange coupling in CrCl$_3$ and CrI$_3$, their common aspects and differences, are investigated on the basis of density functional theory combined with realistic modeling approach for the analysis of interatomic exchange interactions. We perform a comparative study based on the pseudopotential and linear muffin-tin orbital methods by treating the effects of electron exchange and correlation in GGA and LSDA, respectively. The results of ordinary band structure calculations are used in order to construct the minimal tight-binding type models describ…
MXenes are rapidly emerging two-dimensional (2D) materials with thickness, composition, and functionalization-dependent outstanding properties having applications in diverse fields. To disclose nano-spintronic applications of 2D-double transition metal (DTM) carbide and nitride-based pristine and surface-functionalized MXenes (M'2M"X2Tx, M' and M" = Cr, Mo, W; X = C/N; T = -F/-OH/=O), a systematic investigation has been performed on structural stability, magnetic properties and electronic structure using spin-polarized first-principles calculations. 36 stables functionalized MXenes were screen…
Colloidal cobalt-doped TiO2 (anatase) nanocrystals were synthesized and studied by electronic absorption, magnetic circular dichroism, transmission electron microscopy, magnetic susceptibility, cobalt K-shell X-ray absorption spectroscopy, and extended X-ray absorption fine structure measurements. The nanocrystals were paramagnetic when isolated by surface-passivating ligands, weakly ferromagnetic (Ms = 1.5 x 10-3 mB/Co2+ at 300 K) when aggregated, and strongly ferromagnetic (up to Ms = 1.9 mB/Co2+ at 300 K) when spin-coated into nanocrystalline films. X-ray absorption data reveal that cobalt …
In this work we present the magnetic properties of gold coated FePt nanoparticles and the study of stable aqueous dispersions of FePt@Au and FePt synthesized after ligand exchange with mercaptoundecanoic acid. The particle size determined from TEM micrographs goes from 4 nm for the uncoated nanoparticles to a maximum of 10 nm for the gold coated ones indicating that the thickness of the shell ranges from 1 to 3 nm. The magnetic characterization consists in hysteresis cycles at 10 and 300 K. The results show that, at low field and room temperature, the magnetic behavior of uncoated and coated n…
The layered magnetic topological insulator MnBi$_2$Te$_4$ is a promising platform to realize the quantum anomalous Hall effect because its layers possess intrinsic ferromagnetism. However, it is not well understood why the high-spin $d^5$ magnetic ions Mn$^{2+}$ forming the Mn-Te-Mn spin exchange paths prefer ferromagnetic (FM) coupling, contrary to the prediction of the Goodenough-Kanamori rule that a TM-L-TM spin exchange, where TM and L are a transition-metal magnetic cation and a main group ligand, respectively, is antiferromagnetic (AFM) even when the bond angle of the exchange path is 90…
Unprecedented and fascinating phenomena have been recently observed at oxide interfaces between centrosymmetric cubic materials, such as LaAlO$_3$ and SrTiO$_3$, where a polar discontinuity across the boundary gives rise to polarization charges and electric fields that drive a metal-insulator transition, with the appearance of free carriers at the interface. Two-dimensional analogues of these systems are possible, and honeycomb lattices could offer a fertile playground, thanks to their versatility and the extensive on-going experimental efforts in graphene and related materials. Here we sugges…
Prediction of induced magnetism in 2D Ti$_2$C based MXene by manipulating the mixed surface functionalization and metal substitution computed by xTB model Hamiltonian of the DFTB method
Enhancing Hydrogen Adsorption Ability of MOF-5 with Metal Node Exchange and Linker Functionalisation
Carl von Ossietzky Universität Oldenburg（奥尔登堡卡尔·冯·奥西茨基大学）；Friedrich-Schiller Universität Jena（耶拿弗里德里希·席勒大学）；Université de Montpellier, CNRS, ENSCM（蒙彼利埃大学，法国国家科学研究中心，国立化学学院）
Two-dimensional materials (2DM) have attracted much interest due to their distinct optical, electronic, and catalytic properties. These properties can be by tuned a range of methods including substitutional doping or, as recently demonstrated, by surface functionalization with single atoms, increasing even further 2DM portfolio. Here we theoretically and experimentally describe the coordination reaction between MoS$_2$ monolayers with 3d transition metals (TMs), exploring the nature and the trend of MoS$_2$-TMs interaction. Density Functional Theory calculations, X-Ray Photoelectron Spectrosco…
Functionalization of $g$-wave altermagnets: spin-splitter effect enabled by surfaces
Institute for Quantum Materials and Technologies, Karlsruhe Institute of Technology（量子材料与技术研究所，卡尔斯鲁厄理工学院）；Institute of Theoretical Solid State Physics, Karlsruhe Institute of Technology（理论固体物理研究所，卡尔斯鲁厄理工学院）
We have investigated the electronic structure of ZnO:Mn and ZnO:Mn,N thin films using x-ray magnetic circular dichroism (XMCD) and resonance-photoemission spectroscopy. From the Mn 2$p$$\rightarrow3d$ XMCD results, it is shown that, while XMCD signals only due to paramagnetic Mn$^{2+}$ ions were observed in ZnO:Mn, nonmagnetic, paramagnetic and ferromagnetic Mn$^{2+}$ ions coexist in ZnO:Mn,N. XMCD signals of ZnO:Mn,N revealed that the localized Mn$^{2+}$ ground state and Mn$^{2+}$ state hybridized with ligand hole coexisted, implying $p$-$d$ exchange coupling. In the valence-band spectra, spe…
Recently, this long-sought quantum anomalous Hall effect was realized in the magnetic topological insulator. However, the requirement of an extremely low temperature (approximately 30 mK) hinders realistic applications. Based on \textit{ab-initio} band structure calculations, we propose a quantum anomalous Hall platform with a large energy gap of 0.34 and 0.06 eV on honeycomb lattices comprised of Sn and Ge, respectively. The ferromagnetic order forms in one sublattice of the honeycomb structure by controlling the surface functionalization rather than dilute magnetic doping, which is expected …
Based on the density functional theory, we examine the origin of ferromagnetism in the Weyl semimetal Co$_3$Sn$_2$S$_2$ using different types of response theories. We argue that the magnetism of Co$_3$Sn$_2$S$_2$ has a dual nature and bears certain aspects of both itineracy and localization. On the one hand, the magnetism is soft, where the local magnetic moments strongly depend on temperature and the angles formed by these moments at different Co sites of the kagome lattice, as expected for itinerant magnets. On the other hand, the picture of localized spins still remains adequate for the des…
Leveraging coherent light-matter interaction in solids is a promising new direction towards control and functionalization of quantum materials, to potentially realize regimes inaccessible in equilibrium and stabilize new or useful states of matter. We show how driving the strongly spin-orbit coupled proximal Kitaev magnet $α$-RuCl$_3$ with circularly-polarized light can give rise to a novel ligand-mediated magneto-electric effect that both photo-induces a large dynamical effective magnetic field and dramatically alters the interplay of competing isotropic and anisotropic exchange interactions.…
The electronic and magnetic properties of a new diluted magnetic semiconductor (DMS) Ba$_{1-x}$K$_{x}$(Zn$_{1-y}$Mn$_{y}$)$_{2}$As$_{2}$, which is isostructural to so-called 122-type Fe-based superconductors, are investigated by x-ray absorption spectroscopy (XAS) and resonance photoemission spectroscopy (RPES). Mn $L_{2,3}$-edge XAS indicates that the doped Mn atoms have the valence 2+ and strongly hybridize with the $4p$ orbitals of the tetrahedrally coordinating As ligands. The Mn $3d$ partial density of states (PDOS) obtained by RPES shows a peak around 4 eV and relatively high between 0-2…
The first magnetic 2D material discovered, monolayer (ML) CrI$_3$, is particularly fascinating due to its ground state ferromagnetism. Yet, because monolayer materials are difficult to probe experimentally, much remains unresolved about ML CrI$_{3}$'s structural, electronic, and magnetic properties. Here, we leverage Density Functional Theory (DFT) and high-accuracy Diffusion Monte Carlo (DMC) simulations to predict lattice parameters, magnetic moments, and spin-phonon and spin-lattice coupling of ML CrI$_{3}$. We exploit a recently developed surrogate Hessian DMC line search technique to dete…
