Magnetic properties of doped and undoped CuO nanoparticles taking into account spin-phonon interactions

We have studied the influence of doping effects on magnetization M and Neel temperature TN of CuO nanoparticles based on the Heisenberg model including spin-phonon interactions. The experimentally obtained room temperature magnetization M is due to surface or/and doping effects in CuO nanoparticles. We have shown the importance of the effect of the spin-phonon interaction on different properties.     

Anomalies of the phonon properties in multiferroic BiFeO3 thin films near the magnetic phase transition temperature

Size, substrate, doping and magnetic field effects on the phonon properties in multiferroic BiFeO₃ thin films are studied based on a microscopic model. We obtain an anomaly near the magnetic phase transition temperature TN which can be attributed to the magnetoelectric nature of BiFeO₃ and strong anharmonic spin-phonon interaction. It is shown that due to crystal lattice distortion for dopants with ionic radius smaller than that of the host ions the phonon energy decreases (for example Tb or Ti), whereas for the opposite case (larger radius of the doping ions, for example Co or Ni) it increases. The phonon damping is always enhanced compared to the undoped thin film.     

Doping dependent room-temperature ferromagnetism and structural properties of dilute magnetic semiconductor ZnO:Cu nanorods

Copper doped ZnO nanoparticles were synthesized by the chemical technique based on the hydrothermal method. The crystallite structure, morphology and size were determined by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) for different doping percentages of Cu²⁺ (1-10%). TEM/SEM images showed formation of uniform nanorods, the aspect ratio of which varied with doping percentage of Cu²⁺. The wurtzite structure of ZnO gradually degrades with the increasing Cu²⁺ doping concentration and an additional CuO associated diffraction peak was observed above 8% of Cu²⁺ doping. The change in magnetic behavior of the nanoparticles of ZnO with varying Cu²⁺ doping concentrations was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong room-temperature ferromagnetic behavior, however at higher doping percentage of copper the ferromagnetic behavior was suppressed and paramagnetic nature was enhanced.     

Temperature-dependent magnetic anomalies of CuO nanoparticles

Copper oxide (CuO) nanoparticles with an average size of 25 nm were prepared by a sol-gel method. A detailed study was made of the magnetization of CuO nanoparticles using a maximum field of 60 kOe for temperatures between 8 and 300 K. Antiferromagnetic CuO nanoparticles exhibit anomalous magnetic properties, such as enhanced coercivity and magnetic moments. Significantly, the magnitude of the hysteresis component tends to weaken upon increase in temperature (>8 K). In addition, a hysteresis loop shift and coercivity enhancement are observed at 8 K in the field-cooled (FC, at 50 kOe) case. It is thought that the change in hysteresis behavior is due to the uncompensated surface spins of the CuO nanoparticles. The susceptibility (χ) plot showed that χ varied substantially at temperatures below 12 K, and this transition is due to the exchange interactions between the neighboring atoms at the nanoscale.     

Optical phonon modes in a free-standing quantum wire with ring geometry

The confined longitudinal-optical (LO) phonon and surface-optical (SO) phonon modes of a free-standing quantum wire with ring geometry are discussed within the dielectric continuum (DC) approximation. Two branches of SO phonon modes have been investigated. The frequencies of the SO phonons are found to be dispersed and radius dependent for small size systems. When the wave vector qz→∞, the frequencies of each SO modes converge to the frequency values of the single planar heterostructure.     

Effects of electric field and size on the electron-phonon interaction in a spherical quantum dot with impurity

The effects of electric field and size on the electron-phonon interaction with an on-center impurity in a Zn_1?x Cd _x Se/ZnSe spherical quantum dot are studied, taking into account the interactions with confined, half-space and surface optical phonons. In addition, the interaction between impurity and phonons has also been considered. The results show that the electron-confined, electron-half-space, and electron-surface optical phonon interaction energies are all negative. The electron-confined optical phonon interaction energy is weakened by the electric field, but the electron-half-space and electron-surface optical phonon interaction energies are strengthened by it. In particular, the electron-surface optical phonon interaction depends strongly on the electric field, and it will vanish when the electric field is absent. It is also found that the electron-confined optical phonon interaction and electron-impurity “exchange” interaction energies reach a peak values as the quantum dot radius increases and then gradually decrease, but the electron-half-space optical phonon interaction energy exponentially quickly approaches 0 as the quantum dot radius increases.     

Preparation,structural, photoluminescence and magnetic studies of Cu doped ZnO nanoparticles co-doped with Ni by sol–gel method

Zn_0.96−xNi_0.04Cu_xO nanoparticles have been synthesized by varying different Cu concentrations between 0% and 4% using simple sol–gel method. X-ray diffraction studies confirmed the hexagonal structure of the prepared samples. The formation of secondary phases, CuO (111) and Zn (101) at higher Cu content is due un-reacted Cu²⁺ and Zn²⁺ ions present in the solution which reduces the interaction between precursor ions and surfaces of ZnO. Well agglomerated and rod-like structure noticed at Cu=4% greatly de-generate and enhanced the particle size. The nominal elemental composition of Zn, Cu, Ni and O was confirmed by energy dispersive X-ray analysis. Even though energy gap was increased (blue-shift) from Cu=0–2% by quantum size effect, the s–d and p–d exchange interactions between the band electrons of ZnO and localized d electrons of Cu and Ni led to decrease (red-shift) the energy gap at Cu=4%. Presence of Zn–Ni–Cu–O bond was confirmed by Fourier transform infrared analysis. Ultraviolet emission by band to band electronic transition and defect related blue emission were discussed by photoluminescence spectra. The observed optical properties concluded that the doping of Cu in the present system is useful to tune the emission wavelength and hence acting as the important candidates for the optoelectronic device applications. Ferromagnetic ordering of Cu=2% sample was enhanced by charge carrier concentration where as the antiferromagnetic interaction between neighboring Cu–Cu ions suppressed the ferromagnetism at higher doping concentrations of Cu.     

Surface‐enhanced Raman scattering characteristics of CuO : Mn/Ag heterojunction probed by methyl orange: effect of Mn2+ doping

Interest in the synthesis of hybrid substrates for surface‐enhanced Raman scattering (SERS) has surged recently. Hereof, in the present work, a hybrid SERS substrate CuO : Mn/Ag heterojunction has been synthesised. To accomplish this, the nanostructred Ag island film and CuO : Mn nanoparticles are synthesised by vacuum thermal evaporation method and sol–gel method respectively, and thereafter, a heterojunction between the CuO : Mn and Ag is fabricated by adsorption of CuO : Mn (10^‐3 m in ethanol) on Ag island film. Further, the SERS sensitivity of CuO : Mn/Ag heterojunctions has been studied by probing methyl orange. We observed that with Mn‐doping in the lattice of CuO, the SERS signal is enhanced considerably because of ferromagnetic ordering in CuO : Mn. DFT/B3LYP/6‐311 G(d, p) method is used to calculate the energy of HOMO and LUMO level of methyl orange. Copyright © 2016 John Wiley & Sons, Ltd.     

Estimation of contact area of nanoparticles in chains using continuum elastic contact mechanics

In this research, we have studied the doping behaviors of eight transition metal ion dopants on the crystal phase, particle sizes, XRD patterns, adsorption spectra, anatase fraction, and photoreactivity of TiO₂ nanoparticles. The pristine and ion-doped TiO₂ nanoparticles of 15.91-25.47 nm were prepared using sol–gel method. Test metal ion concentrations ranged from 0.00002 to 0.2 at.%. The absorption spectra of the TiO₂ nanoparticles were characterized using UV-Visible spectrometer. The wavelength of the absorption edge of TiO₂ was estimated using the spectra derivative-tangent method. The photoreactivities of pristine and ion-doped TiO₂ nanoparticles under UV irradiation were quantified by the decoloring rate of methyl orange. XRD patterns were recorded using a Rigaku D/MAX-2500 V diffractometer with Cu Kα radiation (50 kV and 250 mA), and particle size and anatase fraction were calculated. Results reveal that different ion doping exhibited complex effects on the studied characteristics of TiO₂ nanoparticles. In general, red shift occurred to ion-doped TiO₂ nanoparticles, but still with higher TiO₂ photoreactivities when doped with Fe³⁺ and Ni²⁺ ions. Among the ions investigated, Ni-doped TiO₂ nanoparticles have shown highest photoreactivity at the concentration of 0.002 at.%, about 1.9 times that of the pristine TiO₂. Ion doping was shown to reduce the diameter and influence the fraction of anatase. Data also indicated that the combination of anatase diameter and ion radius might play an important role in the photoreactivity of TiO₂ nanoparticles. This investigation contributes to the understanding of complex ion doping effects on TiO₂ nanoparticles, and provides references for enhancing their environmental application.     

Effects of ion doping on magnetism of antiferromagnetic nanoparticles

Based on the Heisenberg model including single-ion anisotropy and using a Green's function technique we have studied the influence of doping effects on magnetization M, Neel temperature T_N and coercive field H_c of antiferromagnetic nanoparticles. We have shown that the experimentally obtained room temperature magnetization M is due to surface or/and doping effects in antiferromagnetic nanoparticles.     

Spectral features and antibacterial properties of Cu-doped ZnO nanoparticles prepared by sol-gel method

Zn_(1-x)Cu_x O(x=0.00, 0.01, 0.03, and 0.05) nanoparticles are synthesized via the sol-gel technique using gelatin and nitrate precursors. The impact of copper concentration on the structural, optical, and antibacterial properties of these nanoparticles is demonstrated. Powder x-ray diffraction investigations have illustrated the organized Cu doping into ZnO nanoparticles up to Cu concentration of 5%(x = 0.05). However, the peak corresponding to CuO for x= 0.01 is not distinguishable. The images of field emission scanning electron microscopy demonstrate the existence of a nearly spherical shape with a size in the range of 30–52 nm. Doping Cu creates the Cu–O–Zn on the surface and results in a decrease in the crystallite size. Photoluminescence and absorption spectra display that doping Cu causes an increment in the energy band gap. The antibacterial activities of the nanoparticles are examined against Escherichia coli(Gram negative bacteria)cultures using optical density at 600 nm and a comparison of the size of inhibition zone diameter. It is found that both pure and doped ZnO nanoparticles indicate appropriate antibacterial activity which rises with Cu doping.     

Superconductivity in mesoscopic high-Tc superconducting particles

Based on the Hubbard model in the framework of non-phonon kinematical mechanism and taking into account the discreetness of an electronic energy spectrum, the superconducting critical temperature of a mesoscopic high-T_c sphere is analyzed as a function of doping and as a function of particle's radius. The critical temperature T_c is found to be an oscillating function of the radius of a particle. The size-dependent doping regime is revealed in high-T_c nanoparticles. Our analysis shows that each oscillation in T_c corresponds to the increase in a number of the energy levels in the sphere by 1. The amplitude of oscillations of T_c increases with decreasing R and can reach a value of 6 K for nanoparticles with sizes about 25 nm, in good agreement with experimental studies of YBa₂Cu₃O_7−δ nanoparticles.     

The effects of different doping patterns on the lattice thermal conductivity of solid Ar

In order to investigate the effects of doping patterns on phonon transport, equilibrium molecular dynamics method is performed to calculate the lattice thermal conductivity of solid argon doped with krypton atoms in different geometrical distribution modes. Four different patterns are introduced through replacing Ar atoms with the same amount of Kr atoms in different volume and positions. The simulation results demonstrate that the impurity volume and distribution have significant effects on phonon transport in a crystal structure. The lowest thermal conductivity among the four doping patterns is achieved by introducing the impurity in a nanometer size cubic pattern distributed in the Ar matrix, which is roughly two times lower than that of pure argon at 17 K. The impurity strength on phonons is estimated through comparing the simulation results with those calculated from the Callaway model.     

Synthesis and electrochemical properties of different sizes of the CuO particles

Well-dispersed cupric oxide (CuO) nanoparticles with the size from 10 to 100 nm were successfully synthesized by thermal decomposition of CuC₂O₄ precursor at 400 °C. The prepared CuO nanoparticles of different sizes used as anode materials for Li ion battery all exhibit high electrochemical capacity at the first discharge. However, with the particles size changing, an interesting phenomenon appears. That is, the larger size of the particles is, the discharge capacity of the first time smaller is, while that of the second time is larger. At the same time, the mechanism of the above phenomenon is discussed in this paper. Surprisingly, we have synthesized the copper nanoparticles with different sizes by the CuO of different sizes as the electrodes.     

Origin of the acoustic phonon frequency shifts in semiconducting nanoparticles

The surface and size effects on the acoustic phonon properties of semiconducting nanoparticles, such as ZnO, are studied using the s-d model and a Green's function technique. We have shown that the electron-phonon and anharmonic phonon-phonon interactions play an important role in ZnO nanoparticles and must be taken into account in order to explain the experimental data. Due to surface and size effects on the electron-phonon constants, the acoustic phonon frequency and their damping increase with decreasing of particle size.     

Preparation of CuO nanoparticles by metal salt-base reaction in aqueous solution and their metallic bonding property

This article describes a method for preparing CuO nanoparticles in aqueous solution, and a demonstration of feasibility of metallic bonding with the use of the CuO particles. Colloid solution of CuO nanoparticles was prepared from Cu(NO₃)₂ aqueous solution (0.01 M) and NaOH aqueous solution (0.019 M) at 5–80 °C. Leaf-like aggregates with an average size of 567 nm composed of CuO nanoparticles were produced at 20 °C. The size of leaf-like aggregates decreased with increasing reaction temperature. Metallic copper discs could be bonded using the CuO nanoparticles under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H₂ gas. A shear strength required for separating the bonded discs was 25.4 MPa for the CuO nanoparticles prepared at 20 °C, whose aggregates were the largest among the CuO particles examined. These results indicated that the formation of leaf-like aggregates of CuO nanoparticles led to efficient metallic bonding.     

Effect of nickel doping concentration on structural and magnetic properties of ultrafine diluted magnetic semiconductor ZnO nanoparticles

The ZnO:Ni²⁺ nanoparticles of mean size 2-12 nm were synthesized at room temperature by the simple co-precipitation method. The crystallite structure, morphology and size were determined by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The wurtzite structure of ZnO gradually degrades with the increasing Ni doping concentration and an additional NiO-associated diffraction peak was observed above 15% of Ni²⁺ doping. The change in magnetic behavior of the nanoparticles of ZnO with varying Ni²⁺ doping concentration was investigated using a vibrating sample magnetometer (VSM). Initially, these nanoparticles showed strong ferromagnetic behavior, however, at higher doping percentage of Ni²⁺, the ferromagnetic behavior was suppressed and paramagnetic nature was observed. The enhanced antiferromagnetic interaction between neighboring Ni-Ni ions suppressed the ferromagnetism at higher doping concentrations of Ni²⁺.     

Surface magnetism of nanocrystalline copper monoxide

The effect of the surface on the magnetic susceptibility of nanopowders of the CuO semiconducting antiferromagnet was studied. Single-phase nanopowders with nanoparticles 15, 45, and 60 nm in size were prepared through copper vapor condensation in an argon environment, with subsequent oxidation of the copper. The temperature dependences of the magnetic susceptibility of the nanopowders differ qualitatively from the χ (T) relations for bulk samples. In the region 80≤T≤600 K, the magnetic susceptibility of nanopowders is inversely proportional to temperature and is described by the sum of contributions due to the bulk part of CuO and to the Cu²⁺ paramagnetic ions localized in surface layers. The paramagnetic contribution to the total susceptibility is shown to increase with decreasing particle size and sample density. A comparison of the χ (T) relations is made for nanopowders and for a dense CuO nanoceramic with grain size 5≤d≤100 nm prepared using the shock wave technique.     

Effect of iron doping concentration on magnetic properties of ZnO nanoparticles

The ZnO:Fe nanoparticles of mean size 3-10 nm were synthesized at room temperature by simple co-precipitation method. The crystallite structure, morphology and size estimation were performed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM). The wurtzite structure of ZnO gradually degrades with the increasing Fe doping concentration. The magnetic behavior of the nanoparticles of ZnO with varying Fe doping concentration was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong ferromagnetic behavior, however at higher doping percentage of Fe, the ferromagnetic behavior was suppressed and paramagnetic nature was observed. The enhanced antiferromagnetic interaction between neighboring Fe-Fe ions suppressed the ferromagnetism at higher doping concentrations of Fe. Room-temperature Mössbauer spectroscopy investigation showed Fe³⁺ nature of the iron atom in ZnO matrix.