Sub-100 nm confinement of magnetic nanoparticles using localized magnetic field gradients

Ferromagnetic rods containing thin sections of diamagnetic metal create intense magnetic field gradients that attract and confine magnetic nanoparticles to regions of space as small as 20 nm. The rods (80 nm diameter) comprised alternating sections of CoNi ( approximately 350 nm) and Au (20-160 nm) formed by electrodeposition into porous polycarbonate membranes. Upon magnetizing the rods, large magnetic gradients (106-107 T/m) form at the boundaries between ferromagnetic and diamagnetic sections. These gradients attract and confine magnetic nanoparticles to attoliter volumes of space surrounding the rod. This method provides a new tool for generating intense, highly localized magnetic field gradients, by design, and confining magnetic nanoparticles in these gradients.     

Correlation between Ferromagnetic Layer Easy Axis and the Tilt Angle of Self Assembled Chiral Molecules

The spin–spin interactions between chiral molecules and ferromagnetic metals were found to be strongly affected by the chiral induced spin selectivity effect. Previous works unraveled two complementary phenomena: magnetization reorientation of ferromagnetic thin film upon adsorption of chiral molecules and different interaction rate of opposite enantiomers with a magnetic substrate. These phenomena were all observed when the easy axis of the ferromagnet was out of plane. In this work, the effects of the ferromagnetic easy axis direction, on both the chiral molecular monolayer tilt angle and the magnetization reorientation of the magnetic substrate, are studied using magnetic force microscopy. We have also studied the effect of an applied external magnetic field during the adsorption process. Our results show a clear correlation between the ferromagnetic layer easy axis direction and the tilt angle of the bonded molecules. This tilt angle was found to be larger for an in plane easy axis as compared to an out of plane easy axis. Adsorption under external magnetic field shows that magnetization reorientation occurs also after the adsorption event. These findings show that the interaction between chiral molecules and ferromagnetic layers stabilizes the magnetic reorientation, even after the adsorption, and strongly depends on the anisotropy of the magnetic substrate. This unique behavior is important for developing enantiomer separation techniques using magnetic substrates.     

Magnetic properties of small nickel oxide clusters enclosed inY-zeolite

The magnetization of small nickel oxide clusters containing less than four nickel atoms (sample A) and about ten atoms (sample B), respectively, formed inside the supercages ofY-zeolite, was studied in the magnetic field below 50 kOe and in the temperature range of 2 to 600 K. The magnetic susceptibility of sample A obeyed a Curie-Weiss' (C-W) law above about 20 K with a C-W temperature of 12 K. A saturation behavior was observed in the magnetization versus field (M-H) curve below about 20 K. A hysteresis in the M-H curve and a remanent magnetization were found below about 7 K. A similar behavior was observed for sample B. The observed positive C-W temperature indicates a ferromagnetic interaction between nickel ions in each cluster, which is semiquantitatively consistent with nearest neighbor ferromagnetic interactions previously reported for antiferromagnetic NiO single crystals. The hysteresis suggests an enhanced magnetic anisotropy energy in the present clusters.     

溶剂热法合成花朵状钴磁性粉体及表征

采用一种简单的溶剂热法成功的合成了花朵状的钴磁性粉体。通过X射线粉末衍射(XRD),扫描电子显微镜(SEM)等对样品进行物相与形貌的表征。结果表明样品为六排堆积(hcp)和面心立方结构(fcc)混合结构的钴单质,形貌为由很多个厚度约为50～150 nm的菱形花瓣构成的花朵状结构,每个花朵的尺寸约为2μm左右。采用振动样品磁强计(VSM)测试了样品的磁性能,测试表明样品在室温下表现出铁磁性,饱和磁化强度(Ms)为140 emu.g-1,剩磁(Mr)为9.4 emu.g-1,矫顽力(Hc)为280 Oe。     

Unusual onset of p-element magnetization in a two dimensional structure

Based on density functional theory electronic and magnetic structure characterizations an unusual onset of spin polarization of p states is demonstrated leading to a stable ferromagnetic order within a carbon layered honeycomb-like compound. Specifically structural relaxation of formerly studied C₂N in 3D network and devised here in 2D layered AlB₂-type derived structure shows that the resulting ordered compound maintains the hexagonal crystal symmetry with an exceptionally large c/a ratio leading to strong localization of N states along c and letting magnetization develop within N-p_z orbitals with 1.1 μ_B per formula unit. Anisotropic antibonding interactions between C and N layers allow interpreting the results. The compound is energetically characterized in ferromagnetic ground state versus less stable anti-ferromagnetic order.     

Synthesis of dandelion-like three-dimensional nickel nanostructures via solvothermal route

The objectives of the present research are synthesizing three-dimensional （3D） nickel nanostructures and investigating their magnetic properties. Thus a template-free method was used to prepare 3D dandelion-like nickel nanostructures via reducing of nickel chloride with hydrazine hydrate in ethylene glycol solution at 100 ℃. The resulting Ni nanostructures were characterized by means of powder X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and selected-area electron diffraction （SAED）. And the magnetic properties of the 3D Ni nanostructures were measured as well. Results indicated that solvothermal process could be successfully used to prepare 3D dandelion-like nanostructures of Ni at a relatively mild temperature of 100℃. And the conclusions were made as follows： as-prepared Ni samples had obvious shape anisotropy and were composed of fine nanocrystallites, while they had significantly enhanced ferromagnetic properties than bulk Ni and Ni nanoparticles.     

A novel one-dimensional cyano-bridged Ni3Fe2 ferromagnet constructed from bimetallic molecular squares

Reaction of the complex [Ni(rac-CTH)](2+) (rac-CTH = rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) with [Fe(CN)(6)](3-) leads to a novel cyano-bridged Ni(3)Fe(2) complex, [[Ni(rac-CTH)](3)[Fe(CN)(6)](2)](4). The structure consists of an alternating arrangement of [Fe(CN)(6)Ni(rac-CTH)](2) squares and trans-planar [Ni(rac-CTH)](2+) units bridged by cyanide groups to give a neutral 1D chain running along the a axis. Magnetic measurements reveal the occurrence of ferromagnetic coupling between Fe(III) and Ni(II) ions and 3D magnetic ordering at 3 K due to interchain interactions. Canting of the moments is inferred from the low value of the magnetization of the saturation below T(c).     

Synthesis, nuclear, and magnetic structures and magnetic properties of [Mn3(OH)2(SO4)2(H2O)2

[Mn(3)(OH)(2)(SO(4))(2)(H(2)O)(2)] and its deuterated analogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single-crystal X-ray analysis and Rietveld analysis of neutron powder-diffraction data, consists of a 3D network of chains of edge-sharing Mn(1)O(6), running along the c axis, connected by the apices of Mn(2)O(6) and SO(4) units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long-range ordering (LRO) and short-range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54 degrees towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn(3) trimer, the LRO is achieved by antiparallel alignment of the four symmetry-related trimers within the magnetic unit cell. A spin-flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.     

A combined linear ion trap for mass spectrometry

We propose a novel ion cyclotron resonance ion trap capable of confining ions even at high pressure. The trap consists of three capacitively coupled axial sections, each composed of four circular cross-section rods parallel to the magnetic field axis. Ion confinement along the magnetic field direction is provided by applying the same static voltage to each set of “endcap” rods. As for a two-dimensional quadrupole mass filter, a sufficiently high rf frequency (several MHz) leads to an “effective” electrostatic “pseudopotential” well with a minimum on the trap central axis. Ions are confined radially by the combination of an applied axial static magnetic field and a radially inward-directed electric field resulting from differential rf voltages applied to each set of four rods. Ion confinement properties are revealed from a Paul traplike “stability diagram,” whereas ion trajectories are analyzed in terms of Penning-type ion cyclotron rotation, magnetron rotation, and axial oscillation motional modes. Ion cyclotron frequency increases with the strength of the rf trapping field. Ion magnetron motion becomes stable if the rf voltage is high enough. Therefore, ion trajectories can be stable even in the presence of ion-neutral collisions. Adding an ac potential to a Penning trap should dramatically increase the upper mass detection limit.     

Synthesis, structure and magnetism of a new ferromagnetic hexanuclear nickel cluster with a dicubane-like core

A new ferromagnetic nickel(II) hexameric structure based on the versatile N,O3-ligand 2,2',2"-nitrilotribenzoic acid has been prepared and characterised by X-ray crystallography and magnetic measurements; the compound represents a rare example of a nickel cluster with a dicubane-like core having only oxygen bridges.     

Hydrothermal synthesis in the system Ni(OH)(2)-NiSO(4): nuclear and magnetic structures and magnetic properties of Ni(3)(OH)(2)(SO(4))(2)(H(2)O)(2)

We present the synthesis, characterization by DT-TGA and IR, single crystal X-ray nuclear structure at 300 K, nuclear and magnetic structure from neutron powder diffraction on a deuterated sample at 1.4 K, and magnetic properties as a function of temperature and magnetic field of Ni(3)(OH)(2)(SO(4))(2)(H(2)O)(2). The structure is formed of chains, parallel to the c-axis, of edge-sharing Ni(1)O(6) octahedra, connected by the corners of Ni(2)O(6) octahedra to form corrugated sheets along the bc-plane. The sheets are connected to one another by the sulfate groups to form the 3D network. The magnetic properties measured by ac and dc magnetization, isothermal magnetization at 2 K, and heat capacity are characterized by a transition from a paramagnet (C = 3.954 emu K/mol and theta = -31 K) to a canted antiferromagnet at T(N) = 29 K with an estimated canting angle of 0.2-0.3 degrees. Deduced from powder neutron diffraction data, the magnetic structure is modeled by alternate pairs of Ni(1) within a chain having their moments pointing along [010] and [010], respectively. The moments of Ni(2) atoms are oppositely oriented with respect to their adjacent pairs. The resulting structure is that of a compensated arrangement of moments within one layer, comprising one ferromagnetic and three antiferromagnetic superexchange pathways between the nickel atoms.     

A New Family of Trinuclear Nickel(II) Complexes as Single‐Molecule Magnets

Three new trinuclear nickel (II) complexes with the general composition [Ni₃L₃(OH)(X)](ClO₄) have been prepared in which X=Cl^? ( 1 ), OCN^? ( 2 ), or N₃^? ( 3 ) and HL is the tridentate N,N,O donor Schiff base ligand 2‐[(3‐dimethylaminopropylimino)methyl]phenol. Single‐crystal structural analyses revealed that all three complexes have a similar Ni₃ core motif with three different types of bridging, namely phenoxido (μ₂ and μ₃), hydroxido (μ₃), and μ₂‐Cl ( 1 ), μ_1,1‐NCO ( 2 ), or μ_1,1‐N₃ ( 3 ). The nickel(II) ions adopt a compressed octahedron geometry. Single‐crystal magnetization measurements on complex 1 revealed that the pseudo‐three‐fold axis of Ni₃ corresponds to a magnetic easy axis, being consistent with the magnetic anisotropy expected from the coordination structure of each nickel ion. Temperature‐dependent magnetic measurements indicated ferromagnetic coupling leading to an S=3 ground state with 2J/k=17, 17, and 28 K for 1 , 2 , and 3 , respectively, with the nickel atoms in an approximate equilateral triangle. The high‐frequency EPR spectra in combination with spin Hamiltonian simulations that include zero‐field splitting parameters D_Ni/k=?5, ?4, and ?4 K for 1 , 2 , and 3 , respectively, reproduced the EPR spectra well after a anisotropic exchange term was introduced. Anisotropic exchange was identified as D_i,j/k=?0.9, ?0.8, and ?0.8 K for 1 , 2 , and 3 , respectively, whereas no evidence of single‐ion rhombic anisotropy was observed spectroscopically. Slow relaxation of the magnetization at low temperatures is evident from the frequency‐dependence of the out‐of‐phase ac susceptibilities. Pulsed‐field magnetization recorded at 0.5 K shows clear steps in the hysteresis loop at 0.5–1 T, which has been assigned to quantum tunneling, and is characteristic of single‐molecule magnets.     

室温铁磁性Ni2+掺杂TiO2纳米带的制备与表征

通过水热离子交换方法, 制得不同含量的过渡金属离子Ni2+掺杂的、锐钛矿型的TiO2纳米带. 使用X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM), 高分辨透射电子显微镜(HRTEM), X射线光电子能谱(XPS), 傅立叶变换红外(FTIR)光谱和磁性测试等手段对样品进行了详尽的表征. 结果表明, 经过离子交换, Ni2+离子进入到了TiO2纳米带的晶格中, 其中并没有形成金属Ni团簇或纳米颗粒. 此外, 磁性测试的结果表明, 实验制备的Ni-TiO2样品具有室温铁磁性和磁滞回线特性, 并且, 由于TiO2纳米带中Ni2+离子有较好的分散性, 在相同的外磁场条件下, 样品的磁化强度随着掺杂Ni2+含量的增加而增大.     

A "single-sample concept" (SSC): a new approach to the combinatorial chemistry of inorganic materials

Combinatorial estimations show that, within an unreacted ceramic sample prepared by mixing N different starting materials MxOy with average particle size approximately 1 microm, there are about 10(12) grains per cubic centimeter, sufficient for local reactions to occur that may produce a larger number of product oxides than presently accessible by 2D plate techniques. The "single-sample concept" (SSC) is proposed for performing property-directed syntheses for the preparation of ferri-/ferromagnetic or superconducting compounds. Because of the magnetic properties of the products, libraries of product grains can be sorted by means of magnetic separation techniques. For materials with a large magnetization, the separation efficiency is so high that traces of products can be isolated. The SSC concept was tested experimentally to prepare Fe-based oxides (N=17, 24, 30). The large yields (<75 wt %, N=17) of product grains agree with the literature data, which indicate that 3d metal magnetic oxide phases (Tc>300 K) are most probably Fe oxides. In combination with magnetic separation techniques, SSC seems particularly adapted for exploring the solid-state chemistry of metallic lead elements that form ferri-/ferromagnetic or superconducting oxide phases difficult to detect systematically within the large phase space of theoretically existing compounds.     

Ferromagnetic ordering in a new nickel polyborate NiB12O14(OH)10

A new nickel polyborate, NiB12O14(OH)10 was synthesized using boric acid as a flux. This material has two-dimensional borate layers with a quasi-square lattice of Ni2+. The Ni2+ ions locate in the plane of the two-dimensional layer, bridged through BnO(n+1) chains in the plane and connected with the three-membered ring borate groups out of the plane. The dc and ac magnetic susceptibility, magnetization and specific heat measurements show that this material undergoes a weak ferromagnetic phase transition at Tc = 5.8 K. At T < Tc, a metamagnetic phase transition is observed at about 5 T, associated by a spin-flop, suggesting the ferromagnetic ordering is induced by an antiferromagnetic interaction. A broad maximum in the ac susceptibility at TM = 23-24 K indicates an intermediate short-range ordering.     

Simulation studies of self-assembly of end-tethered nanorods in solution and role of rod aspect ratio and tether length

We present temperature versus concentration phase diagrams for "shape amphiphiles" comprised of tethered moderate and low aspect ratio rods. Simulations of moderate aspect ratio rods (first reported by Horsch et al. [Phys. Rev. Lett. 95, 056105 (2005)]) predict their self-assembly into spherical micelles with bcc order, long micelles with nematic order, a racemic mixture of hexagonally ordered chiral cylinders, two perforated phases: one with tetragonal order and one with hexagonal order, and a smectic C lamellar phase. In contrast, we predict here that small aspect ratio tethered rods self-assemble into bcc ordered spherical micelles, hexagonally ordered cylinders, and a smectic C lamellar phase. We compare and contrast the phases obtained for the two aspect ratios and examine in further detail several unusual phases. Our simulations also reveal that for moderate aspect ratio rods there is a tendency toward phases with decreasing interfacial curvature with decreasing coil size, including a double gyroid phase. In addition, we investigate the role of tether length on the assembled structures. Our results are applicable to short rod-coil block copolymers and rodlike nanoparticles with polymer tethers, and to colloidal building blocks comprised of a flexible string of colloids tethered to a rigid string of colloids, with the interactions scaled appropriately.     

化学溶液沉积法制备自取向BiFeO3多铁薄膜

通过化学溶液沉积法在氧化铟锡(ITO)/导电玻璃上生长了BiFeO₃多晶薄膜.利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱分析仪(XPS)、磁性测量系统(MPMS)和铁电测试仪对样品的结构、形貌、元素价态、铁磁性和铁电性进行研究.结果表明, 薄膜为自取向生长, 具有良好的[101] 生长取向和平整的表面.室温下, 样品呈铁磁性, 沿样品取向方向为易磁化轴方向.铁电测试结果表明, 其饱和电极化强度达到51.3 μC/cm².     

Magnetic anisotropy in Ni(II)-Y(III) binuclear complexes: on the importance of both the first coordination sphere of the Ni(II) ion and the Y(III) ion belonging to the second coordination sphere

The synthesis of a new Ni(II)-Y(III) binuclear complex with a marked elongation axis in the first coordination sphere of the Ni(II) ion is presented. Its zero-field splitting (ZFS) is studied by means of magnetic data and state-of-the-art ab initio calculations. A good agreement between the experimental and theoretical ZFS parameter values is encountered, validating the whole approach. The magnetic anisotropy axes are extracted from the ab initio calculations, showing that the elongation axis around the Ni(II) ion corresponds to the hard axis of magnetization and that the sign of the axial D parameter is imposed by this axis. The Ni-Y axis is found to be an easy axis of magnetization, which is, however, not significant according to the sign of D. The already reported [(H(2)O)Ni(ovan)(2)(μ-NO(3))Y(ovan)(NO(3))]·H(2)O (ovan = o-vanillin) complex is then revisited. In this case, the elongation axis in the Ni(II) coordination sphere is less marked and the ZFS is dominated by the effect of the Y(III) ion belonging to the second coordination sphere. As a consequence, the D parameter is negative and the low-temperature behavior is dominated by the Ni-Y easy axis of magnetization. A competition between the first coordination sphere of the Ni(II) ion and the electrostatic effect of the Y(III) ion belonging to the second coordination sphere is then evidenced in both complexes, and the positive and negative D parameters are then linked to the relative importance of both effects in each complex.     

Canted antiferromagnetism and spin reorientation transition in layered inorganic-organic perovskite (C6H5CH2CH2NH3)2MnCl4

This work presents the synthesis, structure determination and magnetic properties of a new complex, phenethylammonium tetrachloromanganate(II), (C(6)H(5)CH(2)CH(2)NH(3))(2)MnCl(4) (Mn-PEA). Single crystals of Mn-PEA were obtained from methanol solution using the solvent-evaporation method at room temperature. The crystal structure of Mn-PEA was determined by single-crystal X-ray diffraction (orthorhombic, space group Pbca, a = 7.2075(9), b = 7.3012(14), c = 39.413(6) ? and Z = 4). The structure consisted of an extended [MnCl(4)](2-) network and two phenethylammonium cations to form a two-dimensional halide perovskite structure. Temperature-dependent magnetization measurements indicated that Mn-PEA acted as a weak ferromagnet below T(C) = 44.3 K due to spin canting. Below T(C), the magnetic behavior differed significantly from the behavior commonly observed among weak ferromagnets. The susceptibility depended strongly on the crystal orientation, the external magnetic field strength, and the magnetic history. The isothermal magnetization for two orientations revealed a ferromagnetic moment with a spin-canting angle of 0.04° and a spin-flop transitions with H(sf) = 3.5 T. The weak ferromagnetism, which manifested as spontaneous magnetization and magnetic hysteresis near a field strength of zero, was driven by interplay between the easy axis and the antisymmetric Dzyaloshinsky-Moriya (DM) interaction, leading to directional dependent magnetic behavior.