Langmuir-Blodgett self-assembly and electrochemical catalytic property of FePt magnetic nano-monolayer

Dispersed-well FePt nanoparticles with particle size ~5 nm have been prepared by hydrazine hydrate reduction of H₂PtCl₆·6H₂O and FeCl₂·4H₂O in ethanol–water system. By employing as-synthesized FePt nanoparticles, the monolayer can be formed by LB Technique. The structural, magnetic properties and electrochemical properties of FePt monolayer were respectively studied by XRD, TEM, VSM and CHI 820 electrochemical workstation. The as-synthesized particle has a chemically disordered fcc structure and can be transformed into chemically ordered fct structure after annealing treatment above 400°C. The coercivity of ordered fct FePt phase can be up to 2515Oe. CVs of 0.5 M H₂SO₄/0.5M CH₃OH on GCE modified with FePt nanoparticles monolayer films illustrate that the as-synthesized FePt is a kind of active electrochemical catalyst.     

Oriented growth of CoPt nanoparticles by pulsed laser deposition

The magnetic nanoparticles of Fe/FeCo/FePt, in the past, in a PLD system were grown by us using argon ambient gas pressure of about 0.1–75.0 mbar, as the ambient gas pressure can be used to tune the energy of the incident plasma plume species, the expansion volume, the growth duration, etc. which can control the particle size. In present paper, we report the direct synthesis of small-sized nanoparticles even when no ambient gas was used, with the experiments being done in higher vacuum of about 10^?5 mbar in PLD chamber. The deposition rate under vacuum condition is significantly higher than the deposition rate at high ambient pressure. The study of inplane and outplane magnetic properties, along with XRD results, confirmed that the as-deposited CoPt nanoparticles thin film has oriented growth. The as-deposited CoPt nanoparticles are in magnetically soft fcc phase and a post deposition annealing at 600°C resulted in phase transition to magnetically hard fct phase.     

Magnetic and structural characterizations on nanoparticles of FePt,FeRh and their composites

The various compositions of FePt and FeRh nanoparticles, and their composite particles have been fabricated by the solution-phase chemical method and their magnetic properties characterized. High-resolution transmission electron microscopic observations indicate that mono-dispersed FeRh and FePt/FeRh nanoparticles are fabricated with the average size of 3–5 nm. However, larger size particles are distributed in the annealed state. From X-ray diffraction results, the as-deposited FeRh nanoparticles reveal a chemically disordered fcc structure which can be transformed into CsCl-type structure through thermal annealing. Similarly, the annealed FePt nanoparticles show the L1₀-phase fct structure although the fcc structure is apparent in the as-deposited state. It is also found that the first time in the exchange bias effect in the composite of ferromagnetic (FePt) and anti-ferromagnetic (FeRh) nanoparticles; result in a shift of the hysteresis loop after field cooling process.     

Synthesis and characterization of L10 FePt nanoparticles from Pt–Fe3O4 core-shell nanoparticles

Pt/Fe₃O₄ core-shell nanoparticles have been prepared by a modified polyol method. Pt nanoparticles were first prepared via the reduction of Pt(acac)₂ by polyethylene glycol-200 (PEG-200), and layers of iron oxide were subsequently deposited on the surface of Pt nanoparticles by the thermal decomposition of Fe(acac)₃. The nanoparticles were characterized by XRD and HR-TEM. The as-prepared Pt/Fe₃O₄ nanoparticles have a chemically disordered FCC structure and transformed into chemically ordered fct structure after annealing in reducing atmosphere (4% H₂, 96% Ar) at 700 °C. The ordered fct FePt phase has high magnetic anisotropy with coercivity reaching 7.5 kOe at room temperature and 9.3 kOe at 10 K.     

Monolayer deposition of L10 FePt nanoparticles via electrospray route

The deposition monolayers of L1₀ FePt nanoparticles via an electrospraying method and the magnetic properties of the deposited film were studied. FePt nanoparticles in a size of around 2.5 nm in diameter, prepared by a liquid process, were used as a precursor. The size of the deposited particles can be controlled up to 35 nm by controlling the sprayed droplet size that is formed by adjusting the precursor concentration and the precursor flow rate. The droplets were heated in a tubular furnace at a temperature of up to 900 °C to remove all organic compounds and to transform the FePt particles from disordered face centered cubic to an ordered FCT phase. Finally, the particles were deposited in the form of a monolayer film on a silicon substrate by electrostatic force and characterized by scanning electron microscopy. The monolayer of particles was obtained by the high charge on particles obtained during the electrospraying process. The magnetic properties of the monolayer were investigated by magneto-optic Kerr effect measurements. Coercivity up to 650 Oe for a film consisting of 35 nm L1₀ FePt nanoparticles was observed after heat treatment at a temperature of 800 °C.     

Structural and magnetic properties of RF sputtered FePt/Fe multilayers

Series of [FePt(4min)/Fe(t_Fe)]₁₀ multilayers have been prepared by RF magnetron sputtering and post-annealing in order to optimize their magnetic properties by structural designs. The structure, surface morphology, composition and magnetic properties of the deposited films have been characterized by X-ray diffractometer (XRD), Rutherford backscattering (RBS), scanning electron microscope (SEM), energy dispersive X-ray spectroscope (EDX) and vibrating sample magnetometer (VSM). It is found that after annealing at temperatures above 500 °C, FePt phase undergoes a phase transition from disordered FCC to ordered FCT structure, and becomes a hard magnetic phase. X-ray diffraction studies on the series of [FePt/Fe]_n multilayer with varying Fe layer thickness annealed at 500 and 600 °C show that lattice constants change with Fe layer thickness and annealing temperature. Both lattice constants a and c are smaller than those of standard ones, and lattice constant a decreases as Fe layer deposition time increases. Only a slight increase in grain size was observed as Fe layer decreased in samples annealed at 500 °C. However, the increase in grain size is large in samples annealed at 600 °C. The coercivities of [FePt/Fe]_n multilayers decrease with Fe layer deposition time, and the energy product (BH)_max reaches a maximum in the samples with Fe layer deposition time of 3 min. Comparison of magnetic properties with structure showed an almost linear relationship between the lattice constant a and the coercivities of the FePt phase.     

The role of short exchange length in the magnetization processes of L10-ordered FePt perpendicular media

A three-dimensional micromagnetic model with non-uniform grain size distribution has been built up to study the magnetization process in FePt L1₀ perpendicular media. A 3D model of a single FePt magnetic grain is also set up for comparison. The high magneto-crystalline anisotropy K_u results in a short exchange length l_ex in FePt nanograins. Therefore a magnetic grain is divided into smaller grids on the order of l_ex. The simulated perpendicular and longitudinal loops are consistent with experiments, and it is explained why the measured perpendicular H_c is relatively smaller compared with the saturation field of the longitudinal loop in the FePt perpendicular medium.     

Effect of Ni doping on the structural and magnetic properties of FePt nanoparticles

A serial of FePtNi nanoparticles were investigated on their crystal structure and magnetic properties. The FePtNi nanoparticles were synthesized simultaneously by the reduction of iron (III) acetylacetonate, platinum (II) acetylacetonate and nickel (II) acetylacetonate with 1,2-hexadecanediol as the reducing agent. The X-ray diffraction patterns indicate that the addition of 8, 12, 17 at% Ni in FePt nanoparticles suppressed the transformation of the particles from disorder face-centered cubic to order face-centered tetragonal L1₀-phase under annealing treatment. However, further increasing Ni contents to 21 at%, the nanoparticle transformed to L1₂ phase. Doping of Ni into the FePt compound system may decrease coercivity and crystal anisotropy energy. A maximum coercivity of 7 KOe at room temperature was obtained for (Fe₅₂Pt₄₈)₉₂Ni₈ nanoparticles after annealing at 600 °C for 30 min.     

Low-temperature deposition of L10 FePt films for ultra-high density magnetic recording

A method based on strain-induced phase transformation was used to lower the ordering temperature of FePt films. The strain resulted from the lattice mismatch between the FePt film and the substrate or underlayer favored the ordering. The relationships between the lattice mismatch, the ordering of FePt film, and the corresponding magnetic anisotropic constant were investigated. A critical lattice mismatch near 6.33% was believed to be most suitable for improving the chemical ordering of the FePt films. CrX (X=Ru, Mo, W, Ti) alloys with (2 0 0) texture was used to control the easy axis and ordering temperature of FePt films on glass substrate. Large uniaxial anisotropy constant K_u?1×10⁷ erg/cm³, good magnetic squareness (∼1) and FePt(0 0 1) texture (rocking curve −5°) were obtained at the temperature T_s?250 °C when using CrRu underlayer. The diffusion from overlying layers of Ag and Cu and an inserted Ag pinning layer were effective in reducing the exchange decoupling and changing the magnetization reversal. The media noise was effectively reduced and the SNR was remarkably enhanced when a 2 nm Ag was inserted.     

Fabrication of L10 FePtAg nanoparticles and a study of the effect of Ag during the annealing process

L1₀ ferromagnetic phase FePt nanoparticles containing Ag atoms (FePtAg) were synthesized by means of a liquid phase process, followed by annealing. The addition of Ag to FePt nanoparticles permits annealing to be conducted at a lower temperature (350 °C). This is further accompanied by a subsequent transformation in the crystal phase from the FCC superparamagnetic phase to the FCT (L1₀) ferromagnetic phase. The effects of annealing temperature and the Ag atoms inside the nanoparticles on the magnetic properties of the FePt nanoparticles have been studied. Using electron spectroscopy for the chemical analysis (ESCA), Ag atoms in the L1₀ phase FePtAg nanoparticles were found to be localized on the surface region of the annealed nanoparticles. The Ag atoms function to inhibit the oxidation of FePt, causing the particles to become more stable and to have ferromagnetic properties.     

Very high coercivities of top-layer diffusion Au/FePt thin films

The Au/FePt samples were prepared by depositing a gold cap layer at room temperature onto a fully ordered FePt layer, followed by an annealing at 800 °C for the purpose of interlayer diffusion. After the deposition of the gold layer and the high-temperature annealing, the gold atoms do not dissolve into the FePt Ll₀ lattice. Compared with the continuous FePt film, the TEM photos of the bilayer Au(60 nm)/FePt(60 nm) show a granular structure with FePt particles embedded in Au matrix. The coercivity of Au(60 nm)/FePt(60 nm) sample is 23.5 kOe, which is 85% larger than that of the FePt film without Au top layer. The enhancement in coercivity can be attributed to the formation of isolated structure of FePt ordered phase.     

Control of crystallographic orientation in L10 FePt films by using Cr and CrW underlayers

The microstructure and magnetic properties of FePt films grown on Cr and CrW underlayers were investigated. The FePt films that deposited on Cr underlayer show (2 0 0) orientation and low coercivity because of the diffusion between FePt and Cr underlayer. The misfit between FePt magnetic layer and underlayer increases by small addition of W element in Cr underlayer or using a thin Mo intermediate layer, which is favorable for the formation of (0 0 1) orientation and the transformation of FePt from fcc to fct phase. A good FePt (0 0 1) texture was obtained in the films with Cr₈₅W₁₅ underlayer with substrate temperature of 400 °C. The FePt films deposited on Mo/Cr underlayer exhibit larger coercivity than that of the films grown on Pt/Cr₈₅W₁₅ because 5 nm Mo intermediate layer depressed the diffusion of Cr into magnetic layer.     

Enhancement of coercivity with reduced grain size in CoCrPt film grown by pulsed laser deposition

We report a pulsed laser deposition (PLD) growth of VMn/CoCrPt bilayer with a magnetic coercivity (H_c) of 2.2 kOe and a grain size of 12 nm. The effects of VMn underlayer on magnetic properties of CoCrPt layer were studied. The coercivity, H_c, and squareness, S, of VMn/CoCrPt bilayer, is dependent on the thickness of VMn. The grain size of the CoCrPt film can also be modified by laser parameters. High laser fluence used for CoCrPt deposition produces a smaller grain size. Enhanced H_c and reduced grain size in VMn/CoCrPt is explained by more pronounced surface phase segregation during deposition at high laser fluence.     

Decoration of carbon nanotube with size-controlled L10-FePt nanoparticles for storage media

In this work, first multi-wall carbon nanotubes (MWCNTs) with outer diameter about 20–30 nm are synthesized by a CVD method; they have been purified and functionalized with a two-step process. The approach consists of thermal oxidation and subsequent chemical oxidation. Then, monosize FePt nanoparticles along carbon nanotubes surface are synthesized by a Polyol process. The synthesized FePt nanoparticles are about 2.5 nm in size and they have superparamagnetic behavior with fcc structure. The CNTs surfaces as a substrate prevent the coalescence of particles during thermal annealing. Annealing at the temperature higher than 600 ^°C for 2 h under a reducing atmosphere (90 % Ar + 10 % H₂) leads to phase transition from fcc to fct-L1₀ structure. So, the magnetic behavior changes from the superparamagnetic to the ferromagnetic. Furthermore, after the phase transition, the FePt nanoparticles have finite size with an average of about 3.5 nm and the coercivity of particles reaches 5.1 kOe.     

Order-disorder transformation in FePt nanoparticles studied by ferromagnetic resonance

We have investigated the ferromagnetic resonance (FMR) response of as-made and temperature annealed FePt magnetic nanoparticles. The as-made nanoparticles, which have been fabricated by a chemical route, crystallize in the low magnetic anisotropy fcc phase and have a diameter in the range of 2-4 nm. The annealing of the particles at high temperatures (T_A=550, 650 and C) in an inert Ar atmosphere produces a partial transformation to the high magnetocrystalline anisotropy L1₀ phase, with a significant increase in particle size and size distribution. FMR measurements at X-band (9.5 GHz) and Q-band (34 GHz) show a single relatively narrow line for the as-synthesized particles and a structure of two superimposed lines for the three annealed samples. The origin of this line shape has been attributed to the presence of the disordered fcc phase. Assuming that the system consists of a collection of identical particles with a random distribution of easy axes, we have been able to estimate a mean value for the magnetic anisotropy constant of the particles in the fcc phase, K∼2×10⁶ erg/cm³. The measured line shape in the annealed samples can be explained if we consider that the magnetic anisotropy of the particles has a gaussian distribution with a relatively broad width.     

Comparison of nanoparticle measurement instruments for occupational health applications

Nanoparticles are used in many applications because of their novel properties compared to bulk material. A growing number of employees are working with nanomaterials and their exposure to nanoparticles trough inhalation must be evaluated and monitored continuously. However, there is an ongoing debate in the scientific literature about what are the relevant parameters to measure to evaluate exposure to level. In this study, three types of nanoparticles (ammonium sulphate, synthesised TiO₂ agglomerates and aerosolised TiO₂ powder, modes in a range of 30–140 nm mobility size) were measured with commonly used aerosol measurement instruments: scanning and fast mobility particle sizers (SMPS, FMPS), electrical low pressure impactor (ELPI), condensation particle counter (CPC) together with nanoparticle surface area monitor (NSAM) to achieve information about the interrelations of the outputs of the instruments. In addition, the ease of use of these instruments was evaluated. Differences between the results of different instruments can mainly be attributed to the nature of test particles. For spherical ammonium sulphate nanoparticles, the data from the instruments were in good agreement while larger differences were observed for particles with more complex morphology, the TiO₂ agglomerates and powder. For instance, the FMPS showed a smaller particle size, a higher number concentration and a narrower size distribution compared with the SMPS for TiO₂ particles. Thus, the type of the nanoparticle was observed to influence the data obtained from these different instruments. Therefore, care and expertise are essential when interpreting results from aerosol measurement instruments to estimate nanoparticle concentrations and properties.     

Stability Investigation of Colloidal FePt Nanoparticle Systems by Spectrophotometer Analysis

FePt magnetic nanoparticle systems are an excellent candidate for ultrahigh-density magnetic recording. Monodisperse FePt nanoparticles are synthesized by superhydride reduction of FECl2·4H2O and Pt （acac）2 at 263℃ under N2 atmosphere. Transmission electron microscopy （TEM） images show monosize EePt nanoparticles with diameter of 4 nm and a standard deviation of about 10%. The average distance between monodispesre particles is nearly 3 nm, and oleic acid and oleylamine surround the nanoparticles as surfactants. Stability investigation of nanoparticle colloidal solution is done via speetrophotometery analysis. The results for FePt nanoparticles dispersed in hexane indicate that adding surfactants with concentration of 3 × 10^-3 part by volume for centrifugation stage increases the stability of FePt nanoparticles solution with concentration of 16 mg/mL, about 67%.     

Preparation of magnetic nanoparticles by pulsed plasma chemical vapor synthesis

FePt nanoparticle is expected as a candidate for the magnetic material of the high density recording media. We attempted to synthesize FePt alloy nanoparticles using 13.56 MHz glow discharge plasma with the pulse operation of a square-wave on/off cycle of plasma discharge to control the size of nanoparticles. Vapors of metal organics, Biscyclopentadienyl iron (ferrocene) for Fe and (Methylcyclopentadienyl) trimethyl platinum for Pt, were introduced into the capacitively coupled flow-through plasma chamber, which consisted of shower head RF electrode and grounded mesh electrode. Synthesis experiments were conducted at room temperature under the conditions of pressure 0.27 Pa, source gas concentration 0.005 Pa, gas residence time 0.5 s and plasma powers 60 watts. Pulse width for plasma duration was chosen from 0.5 to 30 s and plasma off period was 4 s to each pulse operation. Visual observations during the particle growth showed plasma emission in the bulk region was increased with the particle growth. These were theoretically explained by using the model for both transient particle charging in the plasma and single particle behavior in the stationary plasma as well as assuming the similarity between the negative charged particle and negative gas containing plasma. Synthesized nanoparticles were directly collected onto TEM grid, which was placed just below the grounded mesh electrode in the plasma reactor downstream. TEM pictures showed two kinds of particles in size, one of which was nanometer size and isolated with crystal structures and the other appeared agglomerate of nanometer size particles. The size of agglomerated particle was controlled in the 10–120 nm range by varying the plasma-on time from 0.5 to 30 s, although the nanometer size particles did not change. The composition of FePt alloy particles could be altered by adjusting the source gas feed ratio. Also magnetization of FePt nanoparticles was measured by use of SQUID (superconducting quantum interference device) magnetometry measurements. As-synthesized FePt nanoparticles did not exhibit loop-shape characteristic, which indicated superpamagnetic property. Annealed nanoparticles with the composition of Fe₅₈Pt₄₂ at 650°C in atmospheric hydrogen showed clear hysterisis loop with the coercivity as large as 10 KOe.     

Nanocomposite L10 FePt–SiNx and FePt–SiNx–C films with large coercivity and small grain size on a TiN intermediate layer

FePt–SiN_x–C films with high coercivity, (001) texture and small grain size were obtained by co-sputtering FePt, Si₃N₄ and C on TiN/CrRu/glass substrate at 380 °C. Without C doping, FePt–SiN_x films with good perpendicular anisotropy and a single layer structure were obtained. However, the grain size was still too large and the grain isolation was poor. When C was doped into the FePt–SiN_x films, the out-of-plane coercivity increased due to the decrease of the exchange coupling. In addition, the grain size of the FePt films decreased, and well-separated FePt grains with uniform size were formed. The microstructure of [FePt–SiN_x 40 vol%]−20 vol% C films changed from a single layer structure to a multiple layer structure when the FePt thickness was increased from 4 to 10 nm. By optimizing the sputtering process, the [FePt (4 nm)–SiN_x 40 vol%]−20 vol% C (001) film with coercivity higher than 21.5 kOe, a single layer structure, and small average FePt grain size of 5.6 nm was obtained, which makes it suitable for ultrahigh density perpendicular recording.     

High-resolution transmission electron microscopy investigation of the nanostructure of undoped and Pt-doped nanocrystalline pulsed laser deposited SnO2 thin films

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto alumina substrates. The reactive PLD process was carried out at different substrate deposition temperatures (T_d) between 20 and 600 °C under an oxygen background pressure of 150 mtorr. The same PLD technique was used to produce SnO₂ films in situ-doped with Pt (at the level of ∼2 at. %) through the concomitant ablation of both SnO₂ target and Pt strips. Conventional and high-resolution transmission electron microscopy (HRTEM) observations have revealed that the microstructure of the PLD SnO₂ films is highly sensitive to their deposition temperature. Indeed, its changes from a porous granular structure with extremely fine equiaxed grains (∼4 nm diameter), at T_d=20 °C to a very compact and textured columnar structure characterized by SnO₂ columns (∼25 nm diameter) composed of grains of ∼12 nm of diameter, at T_d=600 °C. In addition, the PLD SnO₂ films were found to exhibit the highest nanoporosity at T_d=300 °C which also coincides with the granular-to-columnar microstructural transition. On the other hand, the microstructure of the Pt-doped SnO₂ films, deposited at 300 °C, was found to contain a high density of defects, such as twin boundaries and edge dislocations. By combining HRTEM and EDS microanalysis, we were able to show that the Pt-dopant self-organizes into spherical nanoparticles (1-2 nm diameter) randomly distributed at the SnO₂ grain boundaries. Finally, doping the films with such platinum nanoclusters is found to affect the SnO₂ nanostructure by particularly reducing the SnO₂ mean grain size (from ∼10 nm when undoped to ∼6 nm for the doped films).