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1.  Structural and thermoelectric properties of TMGa3 (TM = Fe, Co) thin films 
Summary
Based on chemically synthesized powders of FeGa3, CoGa3, as well as of a Fe0.75Co0.25Ga3 solid solution, thin films (typical thickness 40 nm) were fabricated by flash evaporation onto various substrates held at ambient temperature. In this way, the chemical composition of the powders could be transferred one-to-one to the films as demonstrated by Rutherford backscattering experiments. The relatively low deposition temperature necessary for conserving the composition leads, however, to ‘X-ray amorphous’ film structures with immediate consequences on their transport properties: A practically temperature-independent electrical resistivity of ρ = 200 μΩ·cm for CoGa3 and an electrical resistivity of about 600 μΩ·cm with a small negative temperature dependence for FeGa3. The observed values and temperature dependencies are typical of high-resistivity metallic glasses. This is especially surprising in the case of FeGa3, which as crystalline bulk material exhibits a semiconducting behavior, though with a small gap of 0.3 eV. Also the thermoelectric performance complies with that of metallic glasses: Small negative Seebeck coefficients of the order of −6 μV/K at 300 K with almost linear temperature dependence in the range 10 K ≤ T ≤ 300 K.
doi:10.3762/bjnano.4.54
PMCID: PMC3740773  PMID: 23946915
amorphous metal films; energy related; intermetallic compounds; nanomaterials; Seebeck coefficient; thermoelectric properties; thin metal films
2.  Tuning the properties of magnetic thin films by interaction with periodic nanostructures 
Summary
The most important limitation for a significant increase of the areal storage density in magnetic recording is the superparamagnetic effect. Below a critical grain size of the used CoCrPt exchange-decoupled granular films the information cannot be stored for a reasonable time (typically ten years) due to thermal fluctuations arbitrary flipping of the magnetization direction. An alternative approach that may provide higher storage densities is the use of so-called percolated media, in which defect structures are imprinted in an exchange-coupled magnetic film. Such percolated magnetic films are investigated in the present work. We employ preparation routes that are based on (i) self-assembly of Au nanoparticles and (ii) homogeneous size-reduction of self-assembled polystyrene particles. On such non-close-packed nanostructures thin Fe films or Co/Pt multilayers are grown with in-plane and out-of-plane easy axis of magnetization. The impact of the particles on the magnetic switching behavior is measured by both integral magnetometry and magnetic microscopy techniques. We observe enhanced coercive fields while the switching field distribution is broadened compared to thin-film reference samples. It appears possible to tailor the magnetic domain sizes down to the width of an unperturbed domain wall in a continuous film, and moreover, we observe pinning and nucleation at or close to the imprinted defect structures.
doi:10.3762/bjnano.3.93
PMCID: PMC3557708  PMID: 23365796
colloidal lithography; magnetic data storage; magnetic nanostructures; percolated films
3.  Nanoscaled alloy formation from self-assembled elemental Co nanoparticles on top of Pt films 
Summary
The thermally activated formation of nanoscale CoPt alloys was investigated, after deposition of self-assembled Co nanoparticles on textured Pt(111) and epitaxial Pt(100) films on MgO(100) and SrTiO3(100) substrates, respectively. For this purpose, metallic Co nanoparticles (diameter 7 nm) were prepared with a spacing of 100 nm by deposition of precursor-loaded reverse micelles, subsequent plasma etching and reduction on flat Pt surfaces. The samples were then annealed at successively higher temperatures under a H2 atmosphere, and the resulting variations of their structure, morphology and magnetic properties were characterized. We observed pronounced differences in the diffusion and alloying of Co nanoparticles on Pt films with different orientations and microstructures. On textured Pt(111) films exhibiting grain sizes (20–30 nm) smaller than the particle spacing (100 nm), the formation of local nanoalloys at the surface is strongly suppressed and Co incorporation into the film via grain boundaries is favoured. In contrast, due to the absence of grain boundaries on high quality epitaxial Pt(100) films with micron-sized grains, local alloying at the film surface was established. Signatures of alloy formation were evident from magnetic investigations. Upon annealing to temperatures up to 380 °C, we found an increase both of the coercive field and of the Co orbital magnetic moment, indicating the formation of a CoPt phase with strongly increased magnetic anisotropy compared to pure Co. At higher temperatures, however, the Co atoms diffuse into a nearby surface region where Pt-rich compounds are formed, as shown by element-specific microscopy.
doi:10.3762/bjnano.2.51
PMCID: PMC3190617  PMID: 22003453
alloy; Co; CoPt; epitaxy; HRTEM; magnetometry; nanoparticles; Pt; XMCD
4.  Effect of large mechanical stress on the magnetic properties of embedded Fe nanoparticles 
Summary
Magnetic nanoparticles are promising candidates for next generation high density magnetic data storage devices. Data storage requires precise control of the magnetic properties of materials, in which the magnetic anisotropy plays a dominant role. Since the total magneto-crystalline anisotropy energy scales with the particle volume, the storage density in media composed of individual nanoparticles is limited by the onset of superparamagnetism. One solution to overcome this limitation is the use of materials with extremely large magneto-crystalline anisotropy. In this article, we follow an alternative approach by using magneto-elastic interactions to tailor the total effective magnetic anisotropy of the nanoparticles. By applying large biaxial stress to nanoparticles embedded in a non-magnetic film, it is demonstrated that a significant modification of the magnetic properties can be achieved. The stress is applied to the nanoparticles through expansion of the substrate during hydrogen loading. Experimental evidence for stress induced magnetic effects is presented based on temperature-dependent magnetization curves of superparamagnetic Fe particles. The results show the potential of the approach for adjusting the magnetic properties of nanoparticles, which is essential for application in future data storage media.
doi:10.3762/bjnano.2.31
PMCID: PMC3148048  PMID: 21977439
hydrogen in metals; magnetic anisotropy; magnetic data storage; magneto-elastic interactions; nanoparticles; superparamagnetism; thin films
5.  Extended X-ray absorption fine structure of bimetallic nanoparticles 
Summary
Electronic and magnetic properties strongly depend on the structure of the material, especially on the crystal symmetry and chemical environment. In nanoparticles, the break of symmetry at the surface may yield different physical properties with respect to the corresponding bulk material. A useful tool to investigate the electronic structure, magnetic behaviour and local crystallographic structure is X-ray absorption spectroscopy. In this review, recent developments in the field of extended X-ray absorption fine structure measurements and in the analysis methods for structural investigations of bimetallic nanoparticles are highlighted. The standard analysis based on Fourier transforms is compared to the relatively new field of wavelet transforms that have the potential to outperform traditional analysis, especially in bimetallic alloys. As an example, the lattice expansion and inhomogeneous alloying found in FePt nanoparticles is presented, and this is discussed below in terms of the influence of employed density functional theory calculations on the magnetic properties.
doi:10.3762/bjnano.2.28
PMCID: PMC3148049  PMID: 21977436
bimetallic alloys; EXAFS; FePt; nanoparticles; wavelets; XAS
6.  Structural and magnetic properties of ternary Fe1– xMnxPt nanoalloys from first principles 
Summary
Background: Structural and magnetic properties of binary Mn–Pt and ternary Fe1– xMnxPt nanoparticles in the size range of up to 2.5 nm (561 atoms) have been explored systematically by means of large scale first principles calculations in the framework of density functional theory. For each composition several magnetic and structural configurations have been compared.
Results: The concentration dependence of magnetization and structural properties of the ternary systems are in good agreement with previous bulk and thin film measurements. At an intermediate Mn-content around x = 0.25 a crossover between several phases with magnetic and structural properties is encountered, which may be interesting for exploitation in functional devices.
Conclusion: Addition of Mn effectively increases the stability of single crystalline L10 particles over multiply twinned morphologies. This, however, compromises the stability of the ferromagnetic phase due to an increased number of antiferromagnetic interactions. The consequence is that only small additions of Mn can be tolerated for data recording applications.
doi:10.3762/bjnano.2.20
PMCID: PMC3148037  PMID: 21977428
density functional theory; Fe–Pt; magnetic data recording; magnetostructural transition; Mn–Pt
7.  Structure, morphology, and magnetic properties of Fe nanoparticles deposited onto single-crystalline surfaces 
Summary
Background: Magnetic nanostructures and nanoparticles often show novel magnetic phenomena not known from the respective bulk materials. In the past, several methods to prepare such structures have been developed – ranging from wet chemistry-based to physical-based methods such as self-organization or cluster growth. The preparation method has a significant influence on the resulting properties of the generated nanostructures. Taking chemical approaches, this influence may arise from the chemical environment, reaction kinetics and the preparation route. Taking physical approaches, the thermodynamics and the kinetics of the growth mode or – when depositing preformed clusters/nanoparticles on a surface – the landing kinetics and subsequent relaxation processes have a strong impact and thus need to be considered when attempting to control magnetic and structural properties of supported clusters or nanoparticles.
Results: In this contribution we focus on mass-filtered Fe nanoparticles in a size range from 4 nm to 10 nm that are generated in a cluster source and subsequently deposited onto two single crystalline substrates: fcc Ni(111)/W(110) and bcc W(110). We use a combined approach of X-ray magnetic circular dichroism (XMCD), reflection high energy electron diffraction (RHEED) and scanning tunneling microscopy (STM) to shed light on the complex and size-dependent relation between magnetic properties, crystallographic structure, orientation and morphology. In particular XMCD reveals that Fe particles on Ni(111)/W(110) have a significantly lower (higher) magnetic spin (orbital) moment compared to bulk iron. The reduced spin moments are attributed to the random particle orientation being confirmed by RHEED together with a competition of magnetic exchange energy at the interface and magnetic anisotropy energy in the particles. The RHEED data also show that the Fe particles on W(110) – despite of the large lattice mismatch between iron and tungsten – are not strained. Thus, strain is most likely not the origin of the enhanced orbital moments as supposed before. Moreover, RHEED uncovers the existence of a spontaneous process for epitaxial alignment of particles below a critical size of about 4 nm. STM basically confirms the shape conservation of the larger particles but shows first indications for an unexpected reshaping occurring at the onset of self-alignment.
Conclusion: The magnetic and structural properties of nanoparticles are strongly affected by the deposition kinetics even when soft landing conditions are provided. The orientation of the deposited particles and thus their interface with the substrate strongly depend on the particle size with consequences regarding particularly the magnetic behavior. Spontaneous and epitaxial self-alignment can occur below a certain critical size. This may enable the obtainment of samples with controlled, uniform interfaces and crystallographic orientations even in a random deposition process. However, such a reorientation process might be accompanied by a complex reshaping of the particles.
doi:10.3762/bjnano.2.6
PMCID: PMC3045938  PMID: 21977415
epitaxy; iron; magnetic nanoparticles; Ni(111); RHEED; spontaneous self-alignment; STM; W(110); XMCD
8.  Kinetic lattice Monte-Carlo simulations on the ordering kinetics of free and supported FePt L10-nanoparticles 
Summary
The ordering kinetics in free and supported L10 nanoparticles was studied by means of lattice-based kinetic Monte-Carlo simulations. Starting from a fully disordered particle of Wulff shape, the simulations show that the nucleation of ordered domains is starting quickly on various (100) facets but is retarded in the particle volume due to the lack of vacancies compared with a thin film geometry. If a substrate is present, we do not find significant differences in the ordering behavior. This holds true, even if we impose a massively increased thermodynamic driving force for interface segregation, because the nucleation of ordered domains on free facets is significantly faster than the bulk diffusion of the segregating species to the interface. In cases where wetting of the substrate or surface facetting occurs, we find that diffusional atomic motion on the surface goes along with an enhanced long-range order.
doi:10.3762/bjnano.2.5
PMCID: PMC3045943  PMID: 21977414
FePt; Monte-Carlo simulations; nanoparticles; ordering kinetics
9.  Magnetic interactions between nanoparticles 
Summary
We present a short overview of the influence of inter-particle interactions on the properties of magnetic nanoparticles. Strong magnetic dipole interactions between ferromagnetic or ferrimagnetic particles, that would be superparamagnetic if isolated, can result in a collective state of nanoparticles. This collective state has many similarities to spin-glasses. In samples of aggregated magnetic nanoparticles, exchange interactions are often important and this can also lead to a strong suppression of superparamagnetic relaxation. The temperature dependence of the order parameter in samples of strongly interacting hematite nanoparticles or goethite grains is well described by a simple mean field model. Exchange interactions between nanoparticles with different orientations of the easy axes can also result in a rotation of the sub-lattice magnetization directions.
doi:10.3762/bjnano.1.22
PMCID: PMC3045912  PMID: 21977409
dipole interactions; exchange interactions; spin structure; superferromagnetism; superparamagnetic relaxation
10.  Magnetic nanoparticles for biomedical NMR-based diagnostics 
Summary
Rapid and accurate measurements of protein biomarkers, pathogens and cells in biological samples could provide useful information for early disease diagnosis, treatment monitoring, and design of personalized medicine. In general, biological samples have only negligible magnetic susceptibility. Thus, using magnetic nanoparticles for biosensing not only enhances sensitivity but also effectively reduces sample preparation needs. This review focuses on the use of magnetic nanoparticles for in vitro detection of biomolecules and cells based on magnetic resonance effects. This detection platform, termed diagnostic magnetic resonance (DMR), exploits magnetic nanoparticles as proximity sensors, which modulate the spin–spin relaxation time of water molecules surrounding molecularly-targeted nanoparticles. By developing more effective magnetic nanoparticle biosensors, DMR detection limits for various target moieties have been considerably improved over the last few years. Already, a library of magnetic nanoparticles has been developed, in which a wide range of targets, including DNA/mRNA, proteins, small molecules/drugs, bacteria, and tumor cells, have been quantified. More recently, the capabilities of DMR technology have been further advanced with new developments such as miniaturized nuclear magnetic resonance detectors, better magnetic nanoparticles and novel conjugational methods. These developments have enabled parallel and sensitive measurements to be made from small volume samples. Thus, the DMR technology is a highly attractive platform for portable, low-cost, and efficient biomolecular detection within a biomedical setting.
doi:10.3762/bjnano.1.17
PMCID: PMC3045933  PMID: 21977404
biosensor; diagnostics; magnetic nanoparticle; microfluidics; nuclear magnetic resonance
11.  Ultrafine metallic Fe nanoparticles: synthesis, structure and magnetism 
Summary
The results of the investigation of the structural and magnetic (static and dynamic) properties of an assembly of metallic Fe nanoparticles synthesized by an organometallic chemical method are described. These nanoparticles are embedded in a polymer, monodisperse, with a diameter below 2 nm, which corresponds to a number of around 200 atoms. The X-ray absorption near-edge structure and Mössbauer spectrum are characteristic of metallic Fe. The structural studies by wide angle X-ray scattering indicate an original polytetrahedral atomic arrangement similar to that of β-Mn, characterized by a short-range order. The average magnetic moment per Fe atom is raised to 2.59 µB (for comparison, bulk value of metallic Fe: 2.2 µB). Even if the spontaneous magnetization decreases rapidly as compared to bulk materials, it remains enhanced even up to room temperature. The gyromagnetic ratio measured by ferromagnetic resonance is of the same order as that of bulk Fe, which allows us to conclude that the orbital and spin contributions increase at the same rate. A large magnetic anisotropy for metallic Fe has been measured up to (3.7 ± 1.0)·105 J/m3. Precise analysis of the low temperature Mössbauer spectra, show a broad distribution of large hyperfine fields. The largest hyperfine fields display the largest isomer shifts. This indicates a progressive increase of the magnetic moment inside the particle from the core to the outer shell. The components corresponding to the large hyperfine fields with large isomer shifts are indeed characteristic of surface atoms.
doi:10.3762/bjnano.1.13
PMCID: PMC3045918  PMID: 21977400
iron nanoparticles; magnetic properties; organometallic synthesis; size effects; structure
12.  Magnetic coupling mechanisms in particle/thin film composite systems 
Summary
Magnetic γ-Fe2O3 nanoparticles with a mean diameter of 20 nm and size distribution of 7% were chemically synthesized and spin-coated on top of a Si-substrate. As a result, the particles self-assembled into a monolayer with hexagonal close-packed order. Subsequently, the nanoparticle array was coated with a Co layer of 20 nm thickness. The magnetic properties of this composite nanoparticle/thin film system were investigated by magnetometry and related to high-resolution transmission electron microscopy studies. Herein three systems were compared: i.e. a reference sample with only the particle monolayer, a composite system where the particle array was ion-milled prior to the deposition of a thin Co film on top, and a similar composite system but without ion-milling. The nanoparticle array showed a collective super-spin behavior due to dipolar interparticle coupling. In the composite system, we observed a decoupling into two nanoparticle subsystems. In the ion-milled system, the nanoparticle layer served as a magnetic flux guide as observed by magnetic force microscopy. Moreover, an exchange bias effect was found, which is likely to be due to oxygen exchange between the iron oxide and the Co layer, and thus forming of an antiferromagnetic CoO layer at the γ-Fe2O3/Co interface.
doi:10.3762/bjnano.1.12
PMCID: PMC3045930  PMID: 21977399
exchange bias; iron oxide nanoparticles; nanoparticle self-assembly; nanoparticle-thinfilm composite; super-spin glass interaction
13.  Uniform excitations in magnetic nanoparticles 
Summary
We present a short review of the magnetic excitations in nanoparticles below the superparamagnetic blocking temperature. In this temperature regime, the magnetic dynamics in nanoparticles is dominated by uniform excitations, and this leads to a linear temperature dependence of the magnetization and the magnetic hyperfine field, in contrast to the Bloch T 3/2 law in bulk materials. The temperature dependence of the average magnetization is conveniently studied by Mössbauer spectroscopy. The energy of the uniform excitations of magnetic nanoparticles can be studied by inelastic neutron scattering.
doi:10.3762/bjnano.1.6
PMCID: PMC3045916  PMID: 21977393
collective magnetic excitations; Mössbauer spectroscopy; neutron scattering; spin waves; superparamagnetic relaxation
14.  Flash laser annealing for controlling size and shape of magnetic alloy nanoparticles 
Summary
We propose an original route to prepare magnetic alloy nanoparticles with uniform size and shape by using nanosecond annealing under pulsed laser irradiation. As demonstrated here on CoPt nanoparticles, flash laser annealing gives an unprecedented opportunity to control the size and the shape of bimetallic nanoparticles without changing their composition. The mechanisms involved in the complete reshaping of the nanoparticle thin films are discussed and it is also shown that order-disorder phase transformations occur under laser irradiation. This technique is then very interesting for magnetic alloy nanoparticles studies and applications because it opens up a new way to fabricate size-controlled spherical nanoparticles with narrow size dispersion.
doi:10.3762/bjnano.1.7
PMCID: PMC3045924  PMID: 21977394
magnetic alloy nanoparticles; nanoparticle morphology; nanosecond pulsed laser annealing; order-disorder transformation
15.  Review and outlook: from single nanoparticles to self-assembled monolayers and granular GMR sensors 
Summary
This paper highlights recent advances in synthesis, self-assembly and sensing applications of monodisperse magnetic Co and Co-alloyed nanoparticles. A brief introduction to solution phase synthesis techniques as well as the magnetic properties and aspects of the self-assembly process of nanoparticles will be given with the emphasis placed on selected applications, before recent developments of particles in sensor devices are outlined. Here, the paper focuses on the fabrication of granular magnetoresistive sensors by the employment of particles themselves as sensing layers. The role of interparticle interactions is discussed.
doi:10.3762/bjnano.1.10
PMCID: PMC3045928  PMID: 21977397
bottom-up particle synthesis; dipolar particle coupling; granular giant magnetoresistance sensor; magnetic nanoparticles; self-assembly
16.  Preparation and characterization of supported magnetic nanoparticles prepared by reverse micelles 
Summary
Monatomic (Fe, Co) and bimetallic (FePt and CoPt) nanoparticles were prepared by exploiting the self-organization of precursor loaded reverse micelles. Achievements and limitations of the preparation approach are critically discussed. We show that self-assembled metallic nanoparticles can be prepared with diameters d = 2–12 nm and interparticle distances D = 20–140 nm on various substrates. Structural, electronic and magnetic properties of the particle arrays were characterized by several techniques to give a comprehensive view of the high quality of the method. For Co nanoparticles, it is demonstrated that magnetostatic interactions can be neglected for distances which are at least 6 times larger than the particle diameter. Focus is placed on FePt alloy nanoparticles which show a huge magnetic anisotropy in the L10 phase, however, this is still less by a factor of 3–4 when compared to the anisotropy of the bulk counterpart. A similar observation was also found for CoPt nanoparticles (NPs). These results are related to imperfect crystal structures as revealed by HRTEM as well as to compositional distributions of the prepared particles. Interestingly, the results demonstrate that the averaged effective magnetic anisotropy of FePt nanoparticles does not strongly depend on size. Consequently, magnetization stability should scale linearly with the volume of the NPs and give rise to a critical value for stability at ambient temperature. Indeed, for diameters above 6 nm such stability is observed for the current FePt and CoPt NPs. Finally, the long-term conservation of nanoparticles by Au photoseeding is presented.
doi:10.3762/bjnano.1.5
PMCID: PMC3045932  PMID: 21977392
Co; CoPt; core–shell particles; FePt; magnetic anisotropy; magnetic particles; plasma etching; reverse micelles; self-assembly

Results 1-17 (17)