Correlation between physical structure and magnetic anisotropy of a magnetic nanoparticle colloid.

We show the effects of a time-invariant magnetic field on the physical structure and magnetic properties of a colloid comprising 44 nm diameter magnetite magnetic nanoparticles, with a 24 nm dextran shell, in water. Structural ordering in this colloid parallel to the magnetic field occurs simultaneously with the onset of a colloidal uniaxial anisotropy. Further increases in the applied magnetic field cause the nanoparticles to order perpendicular to the field, producing unexpected colloidal unidirectional and trigonal anisotropies. This magnetic behavior is distinct from the cubic magnetocrystalline anisotropy of the magnetite and has its origins in the magnetic interactions among the mobile nanoparticles within the colloid. Specifically, these field-induced anisotropies and colloidal rearrangements result from the delicate balance between the magnetostatic and steric forces between magnetic nanoparticles. These magnetic and structural rearrangements are anticipated to influence applications that rely upon time-dependent relaxation of the magnetic colloids and fluid viscosity, such as magnetic hyperthermia and shock absorption.

Interfacial Symmetry Control of Emergent Ferromagnetism at the Nanoscale.

The emergence of complex new ground states at interfaces has been identified as one of the most promising routes to highly tunable nanoscale materials. Despite recent progress, isolating and controlling the underlying mechanisms behind these emergent properties remains among the most challenging materials physics problems to date. In particular, generating ferromagnetism localized at the interface of two nonferromagnetic materials is of fundamental and technological interest. Moreover, the ability to turn the ferromagnetism on and off would shed light on the origin of such emergent phenomena and is promising for spintronic applications. We demonstrate that ferromagnetism confined within one unit cell at the interface of CaRuO3 and CaMnO3 can be switched on and off by changing the symmetry of the oxygen octahedra connectivity at the boundary. Interfaces that are symmetry-matched across the boundary exhibit interfacial CaMnO3 ferromagnetism while the ferromagnetism at symmetry-mismatched interfaces is suppressed. We attribute the suppression of ferromagnetic order to a reduction in charge transfer at symmetry-mismatched interfaces, where frustrated bonding weakens the orbital overlap. Thus, interfacial symmetry is a new route to control emergent ferromagnetism in materials such as CaMnO3 that exhibit antiferromagnetism in bulk form.

Interface-Driven Ferromagnetism within the Quantum Wells of a Rare Earth Titanate Superlattice.

Here we present polarized neutron reflectometry measurements exploring thin film heterostructures composed of a strongly correlated Mott state, GdTiO_{3}, embedded with SrTiO_{3} quantum wells. Our results reveal that the net ferromagnetism inherent to the Mott GdTiO_{3} matrix propagates into the nominally nonmagnetic SrTiO_{3} quantum wells and tracks the magnetic order parameter of the host Mott insulating matrix. Beyond a well thickness of 5 SrO layers, the magnetic moment within the wells is dramatically suppressed, suggesting that quenched well magnetism comprises the likely origin of quantum critical magnetotransport in this thin film architecture. Our data demonstrate that the interplay between proximate exchange fields and polarity-induced carrier densities can stabilize extended magnetic states within SrTiO_{3} quantum wells.

Electric Field Control of Interfacial Ferromagnetism in CaMnO_{3}/CaRuO_{3} Heterostructures.

New mechanisms for achieving direct electric field control of ferromagnetism are highly desirable in the development of functional magnetic interfaces. To that end, we have probed the electric field dependence of the emergent ferromagnetic layer at CaRuO_{3}/CaMnO_{3} interfaces in bilayers fabricated on SrTiO_{3}. Using polarized neutron reflectometry, we are able to detect the ferromagnetic signal arising from a single atomic monolayer of CaMnO_{3}, manifested as a spin asymmetry in the reflectivity. We find that the application of an electric field of 600 kV/m across the bilayer induces a significant increase in this spin asymmetry. Modeling of the reflectivity suggests that this increase corresponds to a transition from canted antiferromagnetism to full ferromagnetic alignment of the Mn^{4+} ions at the interface. This increase from 1 µ_{B} to 2.5-3.0 µ_{B} per Mn is indicative of a strong magnetoelectric coupling effect, and such direct electric field control of the magnetization at an interface has significant potential for spintronic applications.

Origin of surface canting within Fe3O4 nanoparticles.

The nature of near-surface spin canting within Fe3O4 nanoparticles is highly debated. Here we develop a neutron scattering asymmetry analysis which quantifies the canting angle to between 23° and 42° at 1.2 T. Simultaneously, an energy-balance model is presented which reproduces the experimentally observed evolution of shell thickness and canting angle between 10 and 300 K. The model is based on the concept of Td site reorientation and indicates that surface canting involves competition between magnetocrystalline, dipolar, exchange, and Zeeman energies.

Interfacial ferromagnetism and exchange bias in CaRuO3/CaMnO3 superlattices.

We have found ferromagnetism in epitaxially grown superlattices of CaRuO(3)/CaMnO(3) that arises in one unit cell at the interface. Scanning transmission electron microscopy and electron energy loss spectroscopy indicate that the difference in magnitude of the Mn valence states between the center of the CaMnO(3) layer and the interface region is consistent with double exchange interaction among the Mn ions at the interface. Polarized neutron reflectivity and the CaMnO(3) thickness dependence of the exchange bias field together indicate that the interfacial ferromagnetism is only limited to one unit cell of CaMnO(3) at each interface. The interfacial moment alternates between the 1 µ(B)/interface Mn ion for even CaMnO(3) layers and the 0.5 µ(B)/interface Mn ion for odd CaMnO(3) layers. This modulation, combined with the exchange bias, suggests the presence of a modulating interlayer coupling between neighboring ferromagnetic interfaces via the antiferromagnetic CaMnO(3) layers.

Optimization of spin-triplet supercurrent in ferromagnetic Josephson junctions.

We have observed long-range spin-triplet supercurrents in Josephson junctions containing ferromagnetic (F) materials, which are generated by noncollinear magnetizations between a central Co/Ru/Co synthetic antiferromagnet and two outer thin F layers. Here we show that the spin-triplet supercurrent is enhanced up to 20 times after our samples are subject to a large in-plane field. This occurs because the synthetic antiferromagnet undergoes a "spin-flop" transition, whereby the two Co layer magnetizations end up nearly perpendicular to the magnetizations of the two thin F layers. We report direct experimental evidence for the spin-flop transition from scanning electron microscopy with polarization analysis and from spin-polarized neutron reflectometry. These results represent a first step toward experimental control of spin-triplet supercurrents.

Magnetic correlations of iron oxide nanoparticles as probed by polarized SANS in stretched magnetic nanoparticle-elastomer composites.

We have investigated the magnetic correlations among 7 nm iron oxide nanoparticles embedded in stretched silicone elastomers using polarized Small Angle Neutron Scattering (SANS). The magnetic nanoparticle (MNP)-elastomer composite can be stretched during experiments, and macroscopic deformations cause rearrangement of the iron oxide particles on the nanoscale. Polarized neutrons can be used to nondestructively probe the arrangement of magnetic nanoparticles before and after stretching, so that the relationship between applied stress and nanoscale magnetization can be interrogated. We find that stretching the MNP-elastomer composite past a certain threshold dramatically changes the structural and magnetic morphology of the system. The unstretched sample is modeled well by ~40 nm clusters of ~7 nm particles arranged in a hard sphere packing with a "volume fraction" parameter of 0.3. After the sample is stretched 3× its original size, however, the scattering data can be modeled by smaller, 16 nm clusters with a higher volume fraction of 0.4. We suggest that the effect can be understood by considering a stretching transformation on FCC-like crystallites of iron oxide nanoparticles embedded in an elastomeric medium.

Delta doping of ferromagnetism in antiferromagnetic manganite superlattices.

We demonstrate that delta doping can be used to create a dimensionally confined region of metallic ferromagnetism in an antiferromagnetic (AFM) manganite host, without introducing any explicit disorder due to dopants or frustration of spins. Theoretical consideration of these additional carriers shows that they cause a local enhancement of ferromagnetic double exchange with respect to AFM superexchange, resulting in local canting of the AFM spins. This leads to a highly modulated magnetization, as measured by polarized neutron reflectometry. The spatial modulation of the canting is related to the spreading of charge from the doped layer and establishes a fundamental length scale for charge transfer, transformation of orbital occupancy, and magnetic order in these manganites. Furthermore, we confirm the existence of the canted, AFM state as was predicted by de Gennes [Phys. Rev. 118, 141 (1960)] but had remained elusive.

Core-shell magnetic morphology of structurally uniform magnetite nanoparticles.

A new development in small-angle neutron scattering with polarization analysis allows us to directly extract the average spatial distributions of magnetic moments and their correlations with three-dimensional directional sensitivity in any magnetic field. Applied to a collection of spherical magnetite nanoparticles 9.0 nm in diameter, this enhanced method reveals uniformly canted, magnetically active shells in a nominally saturating field of 1.2 T. The shell thickness depends on temperature, and it disappears altogether when the external field is removed, confirming that these canted nanoparticle shells are magnetic, rather than structural, in origin.

Nearly complete regression of tumors via collective behavior of magnetic nanoparticles in hyperthermia.

One potential cancer treatment selectively deposits heat to the tumor through activation of magnetic nanoparticles inside the tumor. This can damage or kill the cancer cells without harming the surrounding healthy tissue. The properties assumed to be most important for this heat generation (saturation magnetization, amplitude and frequency of external magnetic field) originate from theoretical models that assume non-interacting nanoparticles. Although these factors certainly contribute, the fundamental assumption of 'no interaction' is flawed and consequently fails to anticipate their interactions with biological systems and the resulting heat deposition. Experimental evidence demonstrates that for interacting magnetite nanoparticles, determined by their spacing and anisotropy, the resulting collective behavior in the kilohertz frequency regime generates significant heat, leading to nearly complete regression of aggressive mammary tumors in mice.

Exchange Bias in Bulk α - Fe / γ - Fe 70 Mn 30 Nanocomposites for Permanent Magnet Applications.

Here we report on the microstructural factors influencing the formation of the interfacial exchange bias effect in three-dimensional transition-metal-based nanocomposite systems, with relevance to permanent magnet applications. Bulk phase-separated nanocomposites consisting of the ferromagnetic α -Fe and metastable antiferromagnetic γ - Fe 70 Mn 30 phases exhibit a notable low-temperature exchange bias and substantial coercivity ( H ex = 24.6 kA / m , H C = 95.7 kA / m ) as well as a near room-temperature blocking temperature. Structural investigation by synchrotron X-ray diffraction, neutron scattering, and transmission electron microscopy confirm that the ferromagnetic α -Fe phase nucleates as small precipitates ( d ≈ 50 nm ) at the grain boundaries of the antiferromagnetic γ - Fe 70 Mn 30 grains ( d = 360 - 740 nm ) and grows anisotropically upon heat treatment, resulting in an elliptical geometry. These results indicate that optimization of the exchange bias effect in bulk nanocomposite systems may be achieved through maximizing the surface-to-volume ratio of ferromagnetic precipitates in an antiferromagnetic matrix, enhancing the magnetocrystalline anisotropy of the antiferromagnetic phase to facilitate interfacial pinning and ensuring a balanced distribution of the ferromagnetic and antiferromagnetic phases. This work further clarifies critical factors influencing the formation of an exchange bias in an inexpensive transition-metal-based bulk nanocomposite system with potential for scalable production.

Magnetic Structure Determinations at NBS/NIST.

Magnetic neutron scattering plays a central role in determining and understanding the microscopic properties of a vast variety of magnetic systems, from the fundamental nature, symmetry, and dynamics of magnetically ordered materials to elucidating the magnetic characteristics essential in technological applications. From the early days of neutron scattering measurements at NBS/NIST, magnetic diffraction studies have been a central theme involving many universities, industrial and government labs from around the United States and worldwide. Such measurements have been used to determine the spatial arrangement and directions of the atomic magnetic moments, the atomic magnetization density of the individual atoms in the material, and the value of the ordered moments as a function of thermodynamic parameters such as temperature, pressure, and applied magnetic field. These types of measurements have been carried out on single crystals, powders, thin films, and artificially grown multilayers, and often the information collected can be obtained by no other experimental technique. This article presents, in an historical perspective, a few examples of work carried out at the NIST Center for Neutron Research (NCNR), and discusses the key role that the Center can expect to play in future magnetism research.

Carrier-mediated antiferromagnetic interlayer exchange coupling in diluted magnetic semiconductor multilayers Ga1-xMnxAs/GaAs:Be.

We report the antiferromagnetic (AFM) interlayer exchange coupling between Ga0.97Mn0.03As ferromagnetic semiconductor layers separated by Be-doped GaAs spacers. Polarized neutron reflectivity reveals a characteristic splitting at the wave vector corresponding to twice the multilayer period, indicating that the coupling between the ferromagnetic layers is AFM. When the applied field is increased to above the saturation field, this AFM coupling is suppressed. This behavior is not observed when the spacers are undoped, suggesting that the observed AFM coupling is mediated by doped charge carriers.

Manipulating the magnetic structure of Co core/CoO shell nanoparticles: implications for controlling the exchange bias.

We present an experimental study of the effects of oxidation on the magnetic and crystal structures of exchange biased epsilon-Co/CoO core-shell nanoparticles. Transmission electron microscopy measurements reveal that oxidation creates a Co-CoO interface which is highly directional and epitaxial in quality. Neutron diffraction measurements find that below a Néel temperature TN of approximately 235 K the magnetization of the CoO shell is modulated by two wave vectors, q1=(1/2 1/2 1/2)2pi/a and q2=(100)2pi/a. Oxidation affects the q1 component of the magnetization very little, but hugely enhances the q2 component, resulting in the magnetic decompensation of the core-shell interface. We propose that the large exchange bias effect results from the highly ordered interface between the Co core and CoO shell, and from enhanced core-shell coupling by the uncompensated interface moment.

Nanoscale magnetic structure of ferromagnet/antiferromagnet manganite multilayers.

We use polarized neutron reflectometry and dc magnetometry to obtain a comprehensive picture of the magnetic structure of a series of La(2/3)Sr(1/3)MnO3/Pr(2/3)Ca(1/3)MnO3 (LSMO/PCMO) superlattices, with varying thickness of the antiferromagnetic (AFM) PCMO layers (0

Link between perpendicular coupling and exchange biasing in Fe(3)O(4)/CoOMultilayers.

In studying well-characterized, exchange-biased Fe(3)O(4)/CoO superlattices, we demonstrate a causal link between the exchange bias effect and the perpendicular coupling of the ferrimagnetic and antiferromagnetic spins. Neutron diffraction studies reveal that for thin CoO layers the onset temperature for exchange biasing T(B) matches the onset of locked-in, preferential perpendicular coupling of the spins, rather than the antiferromagnetic ordering temperature T(N). The results are explained by considering the role of anisotropic exchange first proposed by Dzyaloshinsky and Moriya and developing a model based purely on information on structural defects and exchange for these oxides. The devised mechanism provides a general explanation of biasing in systems with perpendicular coupling.

Training effect in an exchange bias system: the role of interfacial domain walls.

Polarized neutron reflectivity (PNR) is used to obtain the magnetic depth profile of an antiferromagnetically coupled ferrimagnetic/ferrimagnetic bilayer, Gd40Fe60/Tb12Fe88. This system shows a transition from positive to negative exchange bias field H(E) as the cooling field H(cf) is increased from small to large positive value. It also exhibits training behavior upon field cycling which affects H(E) and the coercive field H(C). From the PNR measurements at room temperature and at 15 K, we confirm that the magnetic configuration inside the TbFe layer is frozen when the sample is cooled in various H(cf). The thickness and pitch of the magnetic twist inside the TbFe layer depend on H(cf) and give rise to the observed differences in the bias field. Irreversible reorganization of the TbFe magnetization at the interface occurs upon GdFe magnetization reversal and is found to explain the training effect as well as the overall reduction in coercivity.

Pinpointing chiral structures with front-back polarized neutron reflectometry.

A new development in spin-polarized neutron reflectometry enables us to more fully characterize the nucleation and growth of buried domain walls in layered magnetic materials. We applied this technique to a thin-film exchange-spring magnet. After first measuring the reflectivity with the neutrons striking the front, we measure with the neutrons striking the back. Simultaneous fits are sensitive to the presence of spiral spin structures. The technique reveals previously unresolved features of field-dependent domain walls in exchange-spring systems and has sufficient generality to apply to a variety of magnetic systems.