<Emphasis Type="Italic">I–V</Emphasis> behavior of transition metal oxides′ nanoparticles confined in ion tracks

Behavior of transition metal oxide (TMO) nanoparticles (Fe₃O₄, NiO, Co₃O₄, and Mn₃O₄) inserted in ion tracks has been studied in the presence of magnetic field. The special structure of ion tracks in dielectric layer on semiconductors is known as TEMPOS—‘Tunable Electronic Materials with Pores in Oxide on Silicon’. TEMPOS structure offers a high surface to volume ratio resulting in fast response time and high sensitivity of sensors fabricated by inserting suitable materials in the ion tracks. We have already reported the behavior of ferrofluids (aqueous and non-aqueous) inserted in the TEMPOS structures and its feasibility as earth’s magnetic field sensor. In continuation to this study, a comparative study between different transition metal oxides inserted in the ion tracks is being presented here with an aim to understand their response in confined geometry. This study shows that Fe₃O₄ (ferrofluid) is the best choice for ion track-based magnetic field sensor as compared to NiO, Co₃O₄, and Mn₃O₄. Its response to magnetic field can be tailored by the dilution of the ferrofluid and annealing.     

Atomic force microscope studies of CuCl island formation on CaF2(111) substrates

We have grown by molecular beam epitaxy (MBE) CuCl thin films at various thicknesses and substrate temperatures on CaF₂(111) substrates. Atomic force microscope (AFM) topographs reveal that islanding is the dominant growth mechanism. Quantitative analysis of the AFM data enabled us to determine the amount of the substrate remaining exposed after the deposition as well as the total amount of CuCl deposited. We calculated the reciprocal-space height correlation function, 〈 | h(q, t) |each of our films and compared them to the predictions of the shadowing growth theory, which enabled us to extract the important kinetic parameter of surface diffusion length for the growth condition of each of the four films.     

Real‐Time Operation of Photovoltaic Optoelectronic Tweezers: New Strategies for Massive Nano‐object Manipulation and Reconfigurable Patterning

Optical and optoelectronic techniques for micro‐ and nano‐object manipulation are becoming essential tools in nano‐ and biotechnology. Among optoelectronic manipulation platforms, photovoltaic optoelectronic tweezers (PVOTs) are an emergent technique that are particularly successful at producing permanent nanoparticle microstructures. New strategies to enhance the capabilities of PVOT, based on real‐time operation, are investigated. This optoelectronic platform uses z‐cut LiNbO₃:Fe substrates under excitation by a Gaussian light beam. Unexpected results show that during illumination, metallic particles previously deposited on the substrate are ejected from the light spot region. This behavior differs from the trapping phenomenon observed in previous work on PVOT operation, using a sequential method in which illumination is prior to particle manipulation. To discuss the results, a novel mechanism of charge exchange between particles and the ferroelectric substrate is proposed. Applications of this repulsion behavior are investigated. On the one hand, either particle repulsion or trapping in the illuminated region can be obtained by simply light switching on/off. On the other hand, by moving the light spot, different kinds of arbitrarily shaped tracks along the light path, either empty or filled with particles, are obtained. The results demonstrate new key capabilities of PVOT, such as pattern drawing, erasure, and reconfiguration.     

Synthesis of iron oxide nanoparticles under oxidizing environment and their stabilization in aqueous and non-aqueous media

Synthesis of magnetite (Fe₃O₄) nanoparticles under oxidizing environment by precipitation from aqueous media is not straightforward because Fe²⁺ gets oxidized to Fe³⁺ and thus the ratio of Fe³⁺:Fe²⁺=2:1 is not maintained during the precipitation. A molar ratio of Fe³⁺:Fe²⁺ smaller than 2:1 has been used by many to compensate for the oxidation of Fe²⁺ during the preparation. In this work, we have prepared iron oxide nanoparticles in air environment by the precipitation technique using initial molar ratios Fe³⁺:Fe²⁺?2:1. The phases of the resulting powders have been determined by several techniques. It is found that the particles consist mainly of maghemite with little or no magnetite phase. The particles have been suspended in non-aqueous and aqueous media by coating the particles with a single layer and a bilayer of oleic acid, respectively. The particle sizes, morphology and the magnetic properties of the particles and the ferrofulids prepared from these particles are reported. The average particle sizes obtained from the TEM micrographs are 14, 10 and 9 nm for the water, kerosene and dodecane-based ferrofluids, respectively, indicating a better dispersion in the non-aqueous media. The specific saturation magnetization (σ_s) value of the oleic-acid-coated particles (∼53 emu/g) is found to be lower than that for the uncoated particles (∼63 emu/g). Magnetization σ_s of the dodecane-based ferrofluid is found to be 10.1 emu/g for a volume fraction of particles ?=0.019. Zero coercivity and zero remanance on the magnetization curves indicate that the particles are superparamagnetic (SPM) in nature.     

Zinc oxide nano-particles--sonochemical synthesis, characterization and application for photo-remediation of heavy metal

Zinc oxide nanoparticles have been synthesized sonochemically from zinc acetate solution in aqueous methanol, ethanol and iso-propanol containing about 5 volume% of alcohol. Characterization with FESEM, XRD, AFM and BET surface area shows that the synthesized particles differ in shape and size. ZnO synthesized using isopropanol was observed to be the most crystalline one. The synthesized nanoparticles were used for the photocatalytic reduction of hexavalent chromium in aqueous medium under solar radiation. It was observed that the initial reduction rates varied with the difference in morphology of ZnO crystallites.     

Saturation Magnetization and Law of Approach to Saturation for Self-formed Ionic Ferrofluids Based on MnFe2O2 Nanoparticles

测量了MnFe₂O₄纳米微粒及其磁性液体在室温下的磁化曲线.微粒的中值粒径为13.67 nm. 磁性液体的比饱和磁化强度小于理论值.在高场范围(5～10 kOe)下,磁性液体趋于饱和时,其体积分数越大,磁化曲线的斜率越大. 这种饱和磁化强度性质和趋饱和律分别源自于无场时的环状自组装团聚体和场致团聚体. 场致团聚体是耗散结构,以致于其趋饱和磁化律不同于顺磁理论所描述的趋饱和律. 磁性液体中的大微粒导致了表观磁滞现象.     

Ferrite-based magnetic nanofluids used in hyperthermia applications

Magnetic ferrofluids (magnetic nanofluids) have received special attention due to their various biomedical applications such as drug delivery and hyperthermia treatment for cancer. The biological applications impose some special requirements. For example, the well-known iron oxide ferrofluids become undesirable because their iron atoms are poorly distinguishable from those of hemoglobin. A conceivable solution is to use mixed-ferrites (MFe₂O₄ where M=Co, Mn, Ni, Zn) to have a range of magnetic properties. These ferrites have attracted special attention because they save time, and because of their low inherent toxicity, ease of synthesis, physical and chemical stabilities and suitable magnetic properties. Based on the importance of ferrite particles in ferrofluids for hyperthermia treatment, this paper gives a summary on the physical concepts of ferrofluids, hyperthermia principal, magnetic properties and synthesis methods of nanosized ferrites.     

The modulation of coupling in the relaxation behavior of light transmitted through binary ferrofluids

With an external magnetic field, a relaxation process is observed when the light transmit through binary ferrofluids composed of ferrimagnetic CoFe₂O₄ and paramagnetic p-NiFe₂O₄ nanoparticles similar to ferrofluids consisting only of CoFe₂O₄. Since only the ferrimagnetic nanoparticles are able to form field-induced chainlike structures for such binary ferrofluids by magnetic interaction between the particles, so the relaxation behavior of the transmitted light is caused mainly by the ferrimagnetic system. In the binary ferrofluids, the paramagnetic nanoparticles, regarded as magnetically polarized gas molecules, are restrained to occupy the space between the ferrimagnetic chains and distribute following the CoFe₂O₄ particle chains covering and diverging, producing a modulation effect on the relaxation behavior of the transmitted light. The modulation effect can be characterized by range and time parameters that describe the relationship of the relaxation behavior of the transmitted light to the properties of the binary ferrofluids and single CoFe₂O₄ ferrofluids.     

A magnetic field-dependent modulation effect tends to stabilize light transmission through binary ferrofluids

In binary ferrofluids composed of ferromagnetic γ?Fe₂O₃/Ni₂O₃ composite nanoparticles (A particles) and noncrystalline Fe₂O₃ nanoparticles (B particles), the A particles alone will form chain-like aggregates upon application of a magnetic field. Due to both the long-range ‘magnetic convergent force’ (F_C) and the short-range ‘magnetic divergent force’ (F_D), the A-particle chains immersed in the B-particle ‘sea’ will move in a manner similar to the process of vibrational damping. The apparent damping of the ferrofluids will vary from weak to overdamping according to the motion of the chains, so that the intensity of light transmitted through a ferrofluid film along the direction of the field would tend to stabilize after a period of rapid decrements and increments. In binary ferrofluids, the B-particle system can produce a modulation effect on both the damping and the driving force, further stabilizing the behavior of the transmitted light. At low fields (e.g., 500 Gs, 900 Gs) only the modulation of the viscosity drag force (F_v) is considerable, so that overdamping increases linearly with B-particle volume fraction (Ф_B), and the variation in the transmitted light is much slower during the process tending towards stability as Ф_B increases. However, at high fields (e.g., 1300 Gs) the polarization of the B-particle ‘sea’ is enhanced, so that F_D is modulated as well as F_v (i.e., both the practical damping and driving forces are modulated simultaneously). Thus, the apparent overdamping of the binary ferrofluids system will vary non-linearly as Ф_B increases, and the transmitted light will tend to stabilize faster for ferrofluids with high Φ_B than for those with low Ф_B at an applied magnetic field of 1300 Gs.     

Synthesis and structural investigation of ferrofluids with porphyrins and prospects of their application in photodynamic therapy

Complexes of superparamagnetic nanoparticles of magnetite with porphyrins, i.e., sulfonated tetraphenylporphine dihydrochloride (H₂TPPS₄(HCl)₂) and photodithazine (used in photodynamic therapy for treatment of oncological diseases), in an aqueous medium have been synthesized for the first time and investigated using small-angle neutron scattering and spectrophotometry. The influence of the biocompatible polymer Pluronic on the functional properties of the synthesized complexes has also been analyzed. It has been shown that the synthesized complexes of ferrofluids with photodithazine and Pluronic exhibit a high efficiency as compounds capable of suppressing the reproduction of tumor cell cultures. The results obtained can be used in the design of a magnetically guided drug for photodynamic therapy.     

Magnetic colloidal properties of ionic ferrofluids

Magnetic properties of colloidal suspensions of γ-Fe₂O₃ particles, obtained through a chemical synthesis, are investigated. Using an optical technique it is verified that these ionic aqueous ferrofluids are stable in high fields. The magnetization saturation of the particles is found independent of their size. Electron microscopy, magnetization and birefringence measurements allow us to separate the two superparamagnetic processes existing in such ferrofluid solutions: Bulk and Néel rotations. The Néel process is investigated through remanent magnetization of frozen solution.     

Influence of Si substrate preparation on surface chemistry and morphology of L-CVD SnO2 thin films studied by XPS and AFM

Results of experimental studies of the influence of substrate preparation on the surface chemistry and surface morphology of the laser-assisted chemical vapour deposition (L-CVD) SnO₂ thin films are presented in this paper. The native Si(1 0 0) substrate cleaned by UHV thermal annealing (TA) as well as thermally oxidized Si(1 0 0) substrate cleaned by ion bombardment (IBA) have been used as the substrates. X-ray photoemission spectroscopy (XPS) has been used for the control of surface chemistry of the substrates as well as of deposited films. Atomic force microscopy (AFM) has been used to control the surface morphology of the L-CVD SnO₂ thin films deposited on differently prepared substrates. Our XPS shows that the L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit the same stoichiometry, i.e. ratio [O]/[Sn] = 1.30 as that of the layers deposited on Si(1 0 0) substrate previously cleaned by UHV prolonged heating. AFM shows that L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit evidently increasing rough surface topography with respect to roughness, grain size range and maximum grain height as the L-CVD SnO₂ thin films deposited on atomically clean Si substrate at the same surface chemistry (nonstoichiometry) reflect the higher substrate roughness after cleaning with ion bombardment.     

Study of polydiethylsiloxane-based ferrofluid with excellent frost resistance property

The polydiethylsiloxane-based ferrofluid was prepared by dispersing finely divided magnetic Fe₃O₄ particles which are modified with oleoyl sarcosine and lauroyl sarcosine. The optimized experiment parameters including molar ratio of surfactant to Fe₃O₄ (1:5), temperature (80 °C), stirring rate (300 RPM), the surfactant content of lauroyl sarcosine (0 to 33 mol%) and the modification time (25 min) were obtained by the orthogonal test. The magnetic liquid was characterized by a transmission electron microscope (TEM), infrared (IR) spectrometer, X-ray diffractometer (XRD), thermogravimetry (TG), vibrating sample magnetometer (VSM) and differential scanning calorimetry (DSC). It is indicated that the surfactant is mainly bonded to the surface of Fe₃O₄ nanoparticles through covalent bond between carboxylate (COO⁻) and Fe atom. The modified magnetic particles are equally dispersed into the carrier and remain stable below −12 °C over 4 months. The ferrofluids exhibit excellent frost resistance property and distinctly reduced temperature coefficient of viscosity compared with polydimethylsiloxane-based ferrofluids and hydrocarbon-based ferrofluids, respectively. The saturation magnetization could reach up to 27.7 emu/g.     

Sensitized luminescence of Eu and Tb macrocyclic complexes bearing benzophenone antennae

Sensitized luminescence behavior of lanthanide (Ln=Eu³⁺, Tb³⁺) macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) complexes bearing one or four benzophenone (BP) moieties as antenna (LnL1 and LnL4) has been studied in water. Despite higher molar extinction coefficient of EuL4 owing to four antennae, it shows only one-thirtieth the luminescence intensity of EuL1. Energy level of triplet excited-state of BP antenna (E_T) is only a few kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺, thus promoting a back energy transfer (BET) from ⁵D₂ of Eu³⁺ to ground-state BP antennae. On EuL4 bearing four antennae, BET occurs more rapidly than that on EuL1, thus exhibiting much weaker luminescence. For Tb complexes, the energy gap between E_T of BP antenna and ⁵D₄ excited state of Tb³⁺ is large enough (>13 kJ mol⁻¹), such that practically no BET occurs. The luminescence intensity of TbL4 is, however, lower (two-third) than that of TbL1. Time-resolved luminescence measurement reveals that hydration number of Tb³⁺ within TbL4 is twice that within TbL1. This is because the structural distortion of ligands on TbL4, caused by an intramolecular dipole-dipole interaction among the BP antennae, allows coordination of higher number of H₂O molecules to Tb³⁺, thus leading to a strong Tb luminescence quenching via O-H oscillators.     

Sensitized luminescence properties of dinuclear lanthanide macrocyclic complexes bearing a benzophenone antenna

Dinuclear lanthanide (Ln=Tb³⁺ or Eu³⁺) complexes (Ln₂L2) of two octadentate macrocyclic polyaminopolycarboxylic ligands connected through a benzophenone (BP) moiety (L2) have been synthesized. Sensitized luminescence properties of Ln₂L2 in water have been studied in comparison to those of BP-conjugated mononuclear Ln complexes (LnL1). The luminescence intensity of Tb₂L2 is lower than that of TbL1 because of lower triplet quantum yield of the BP moiety. In contrast, Eu₂L2 shows higher intensity than EuL1. For both Eu complexes, energy level of triplet excited-state BP (³BP*) is only 3 kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺. The ⁵D₂ state formed by a triplet-energy transfer (TET) from ³BP* is therefore deactivated by a back energy transfer (BET) to the ground-state BP, resulting in low luminescence intensity of EuL1. In contrast, within Eu₂L2, TET from ³BP* to ⁵D₀ state of two Eu³⁺ ions is accelerated, thus leading to higher luminescence intensity. Another notable feature of Eu₂L2 is the luminescence quantum yield independent of its concentration. In contrast, for EuL1 system, an intermolecular BET occurs from ⁵D₂ state of Eu³⁺ to the ground-state BP conjugated to another EuL1 complex, resulting in a yield decrease with the concentration increase.     

Effect of the group IV elements on the Π anion and cation states of thiophene and furan determined by means of ETS and UPS

The electron-transmission and He(I) photoelectron spectra of Si(CH₃)₃, Sn(CH₃)₃ and CH₂Si(CH₃)₃ derivatives of thiophene and furan have been recorded. The first two substituents perturb the energies of the outer filled π orbitals and of the empty π* orbitals in opposite directions, causing a reduction of the HOMO/LUMO energy separation. The stabilization experienced by the π* MO's depends on their wavefunction coefficients at the site of substitution, and is attributed to interaction with low-lying empty orbitals of the substituent groups. The relatively small size (～ 0.4 eV) of this effect on the unoccupied ring MO's suggests that it should not appreciably affect the energy of the filled MO's.The strong conjugation between the π* unoccupied orbital of the nitro group and those of thiophene has also been investigated.     

The modification effect in magnetization behaviors for CoFe2O4–p-NiFe2O4 binary ferrofluids

The magnetization curves of CoFe₂O₄ ferrofluids, p-NiFe₂O₄ paramagnetic fluids and CoFe₂O₄–p-NiFe₂O₄ binary ferrofluids, in which the volume fraction of CoFe₂O₄ particles φ _Co is 0.6% and one of p-NiFe₂O₄ particles φ _Ni is 0.2%, 0.4%, 0.6% and 0.8% respectively, prepared by the Massart method, have been measured at room temperature. Comparison of the experimental data from the CoFe₂O₄ ferrofluids with the Langevin theory curves demonstrates a considerable difference between them, but a curve fitted using a model of a gas-like compression (MGC) agrees with the experimental data very well. The experimental results show that the magnetization of the CoFe₂O₄–p-NiFe₂O₄ binary ferrofluid is not a simple summation of the ferrimagnetic CoFe₂O₄ part and the paramagnetic p-NiFe₂O₄ part. From the fitted results, it was found that the saturation magnetization of the CoFe₂O₄ part of the binary ferrofluid depends non-monotonically on the p-NiFe₂O₄ particle volume fraction, and the CoFe₂O₄ part is a stronger “hard” magnet than CoFe₂O₄ in simple ferrofluids. The magnetization behavior of the binary ferrofluids is explained by the modification of the microstructure of CoFe₂O₄ nanoparticle system by the p-NiFe₂O₄ nanoparticle system.     

A study of modified Fe3O4 nanoparticles for the synthesis of ionic ferrofluids

XRD and XPS analyses revealed that a Fe(NO₃)₃·9H₂O layer formed outside γ-Fe₂O₃ particles when Fe₃O₄ nanoparticles were treated with ferric nitrate. The particle density differed for untreated and treated particles and was not uniform for the latter. The specific saturation magnetization of both treated and untreated particles was used to estimate the thickness of the Fe(NO₃)₃·9H₂O layer and the average density of the treated particles. The density of the treated particles was used to calculate the density of ferrofluids of different particle volume fractions. These values are in agreement with measured results. Therefore, the particle volume fraction can be designed to synthesize acid ionic ferrofluids based on Fe₃O₄ nanoparticles using Massart's method.     

Synthesis of aqueous ferrofluids of ZnxFe3−xO4 nanoparticles by citric acid assisted hydrothermal-reduction route for magnetic hyperthermia applications

Superparamagnetic and monodispersed aqueous ferrofluids of Zn substituted magnetite nanoparticles (Zn_xFe_3−xO₄, x=0, 0.25, 0.3, 0.37 and 0.4) were synthesized via hydrothermal-reduction route in the presence of citric acid, which is a facile, low energy and environmental friendly method. The synthesized nanoparticles were characterized by X ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and the dynamic light scattering (DLS) method. The results showed that a certain amount of citric acid was required to obtain single phase Zn substituted magnetite nanoparticles. Citric acid acted as a modulator and reducing agent in the formation of spinel structure and controlled nanoparticle size and crystallinity. Mean particle sizes of the prepared nanoparticles were around 10 nm. The results that are obtained from XRD, magnetic and power loss measurements showed that the crystallinity, saturation magnetization (M_S) and loss power of the synthesized ferrofluids were all influenced by the substitution of Zn in the structure of magnetite. The Zn substituted magnetite nanoparticles obtained by this route showed a good stability in aqueous medium (pH 7) and hydrodynamic sizes below 100 nm and polydispersity indexes below 0.2. The calculated intrinsic loss power (ILP) for the sample x=0.3 (e.g. 2.36 nH m²/kg) was comparable to ILP of commercial ferrofluids with similar hydrodynamic sizes.     

Calibration of CR-39 with atomic force microscope for the measurement of short range tracks from proton-induced target fragmentation reactions

We studied the track response of CR-39 plastic nuclear track detectors (PNTD) for low (<6 MeV/n) and high (>100 MeV/n) energy heavy ions using the atomic force microscope (AFM). CR-39 PNTD was exposed to several heavy ion beams of different energy at HIMAC (Heavy Ion Medical Accelerator in Chiba). For AFM measurement, the amount of bulk etch was controlled to be ∼2 μm in order to avoid etching away of short range tracks. The response data obtained by AFM for ∼2 μm bulk etch was in good agreement with data obtained by the conventional optical microscope analysis for larger bulk etch. The response data from low energy beams (stopping near the surface) was also consistent with the data from high energy beams (penetrating the detector) as a function of REL (restricted energy loss) with the δ-ray cut off energy of ω₀ = 200 eV. We experimentally verified that REL (ω₀ = 200 eV) gives a universal function for wide energy range in CR-39 PNTD. This work has been done as part of a basic study in the measurement of secondary short range tracks produced by target fragmentation reactions in proton cancer therapy fields.