First-Principles Study of Magnetic Properties of 3d Transition Metals Doped in ZnO Nanowires

The defect formation energies of transition metals (Cr, Fe, and Ni) doped in the pseudo-H passivated ZnO nanowires and bulk are systematically investigated using first-principles methods. The general chemical trends of the nanowires are similar to those of the bulk. We also show that the formation energy increases as the diameter of the nanowire decreases, indicating that the doping of magnetic ions in the ZnO nanowire becomes more difficult with decreasing diameter. We also systematically calculate the ferromagnetic properties of transition metals doped in the ZnO nanowire and bulk, and find that Cr ions of the nanowire favor ferromagnetic state, which is consistent with the experimental results. We also find that the ferromagnetic coupling state of Cr is more stable in the nanowire than in the bulk, which may lead to a higher T (c) useful for the nano-materials design of spintronics.

Structure, magnetization, and low-temperature spin dynamic behavior of zincblende Mn-rich Mn(Ga)As nanoclusters embedded in GaAs

We have fabricated a set of samples of zincblende Mn-rich Mn(Ga)As clusters embedded in GaAs matrices by annealing (Ga,Mn)As films with different nominal Mn content at 650 degrees C. For the samples with Mn content no more than 4.5%, the Curie temperature reaches nearly 360 K. However, when Mn content is higher than 5.4%, the samples exhibit a spin-glass-like behavior. We suggest that these different magnetic properties are caused by the competing result of dipolar and Ruderman-Kittel-Kasuya-Yosida interaction among clusters. The low-temperature spin dynamic behavior, especially the relaxation effect, shows the extreme creeping effect which is reflected by the time constant tau of similar to 10(11) s at 10 K. We explain this phenomenon by the hierarchical model based on the mean-field approach. We also explain the memory effect by the relationship between the correlation function and the susceptibility.

Effects of crystalline quality on the ultraviolet emission and electrical properties of the ZnO films deposited by magnetron sputtering

The ZnO films were deposited on c-plane sapphire, Si (0 0 1) and MgAl2O4 (1 1 1) substrates in pure Ar ambient at different substrate temperatures ranging from 400 to 750 degrees C by radio frequency magnetron sputtering. X-ray diffraction, photoluminescence and Hall measurements were used to evaluate the growth temperature and the substrate effects on the properties of ZnO films. The results show that the crystalline quality of the ZnO films improves with increasing the temperature up to 600 degrees C, the crystallinity of the films is degraded as the growth temperature increasing further, and the ZnO film with the best crystalline quality is obtained on sapphire at 600 degrees C. The intensity of the photoluminescence and the electrical properties strongly depend on the crystalline quality of the ZnO films. The ZnO films with the better crystallinity have the stronger ultraviolet emission, the higher mobility and the lower residual carrier concentration. The effects of crystallinity on light emission and electrical properties, and the possible origin of the n-type conductivity of the undoped ZnO films are also discussed. (C) 2009 Elsevier B. V. All rights reserved.

The electronic structure of strained ZnO/MgxZn1-xO superlattices and the influence of polarization

Based on the effective-mass model, the lower energies of the electron and the hole of ZnO/MgxZn1-xO superlattices are calculated. Because of the mismatch of the lattice constant between the ZnO well and the MgxZn1-xO barrier, piezoelectric and spontaneous polarization exist in ZnO/MgxZn1-xO superlattices and a macroscopical internal electric held is found when well width L-w >4 nm and Mg concentration x > 0.2. The parameters of ZnO/MgxZn1-xO superlattices such as lattice constant, band offset, etc. are also proposed. Through calculations, we found the internal electric field can change the lowest energies of the electron and hole to 105.4 and 85.1 meV when well width L-w up to 70 angstrom, which will influence the electronic and optical properties of ZnO/MgxZn1-xO superlattices greatly, while the Rashba effect from the internal electric field is so small that it can be neglected. The ground state exciton energies with different Mg concentration x are also calculated by variational method, our results are very close to the experimental results when Mg concentration x <= 0.3. (C) 2008 Elsevier B.V. All rights reserved.

Magnetic properties of ZnO-doped cobalt ferrite

The cobalt ferrites with chemical composition Co1+xZnxFe2-2xO4 (r=0.0, 0.1, 0.2, 0.4) were obtained with conventional solid reaction. The ZnO-doped samples have lower lattice constant than CoFe2O4 by adjusting Co ions to the octahedral sites. The results show that doping ZnO could extremely improve the magnetic properties. In comparison with pure CoFe2O4, the little ZnO-doped sample has higher permeability and much lower coercivity at the condition of a little decrease of magnetization saturation. Sample with x=0.1 shows evident magnetostrictive effect at the magnetic field of 30-60 mT while pure cobalt ferrite sample does not, though the saturation magnetostriction decreases. These indicate that ZnO-doping improves the magnetostrictive sensitivity of the cobalt ferrites and have potential applications in magnetoelectric devices and magnetic detector.

Growth of c-oriented ZnO films on (001) SMO3 substrates by MOCVD

The growth direction of ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD) is modulated by pretreatment of (001) SMO3 (STO) substrates. ZnO films show a-oriented smooth surface with epitaxial relationship of < 001 > ZnO//< 110 > STO on as-received SfO, and c-axis columnar growth with < 010 > ZnO//< 110 > STO on etched STO, respectively. The orientation alteration of ZnO films is supposed to be caused by the change of STO surface polarity. In addition, the c-ZnO films exhibit an enhanced photoluminescence (PL) intensity due to the improved crystal quality, while the blueshift of PL peak is attributed to the smaller tensile strain. These results show that high quality c-ZnO, which is essential for electronic and optoelectronic device applications, can be grown on (001) SfO by MOCVD. (C) 2008 Elsevier B.V. All rights reserved.

Growth Parameter Dependence of Structural Characterizations of Diluted Magnetic Semiconductor (Ga, Cr)As

We report the influence of growth parameters and post-growth annealing on the structural characterizations and magnetic properties of (Ga, Cr)As films. The crystalline quality and magnetic properties are sensitive to the growth conditions. The single-phase (Ga, Cr)As film with the Curie temperature of 10 K is synthesized at growth temperature T-s = 250 degrees C and with nominal Cr content x = 0.016. However, for the films with x > 0.02, the aggregation of Cr atoms is strongly enhanced as both T. and x increase, which not only brings strong compressive strain in the epilayer, but also roughens the surface. The origin of room-temperature ferromagnetism in (Ga, Cr)As films with nanoclusters is also discussed.

Strain status in ZnO film on sapphire substrate with a GaN buffer layer grown by metal-source vapor phase epitaxy

ZnO film of 8 mu m thickness was grown on a sapphire (0 0 1) substrate with a GaN buffer layer by a novel growth technique called metal-source vapor phase epitaxy (MVPE). The surface of ZnO film measured by scanning electron microscope (SEM) is smooth and shows many regular hexagonal features. The full width at half maximum (FWHM) of ZnO(0 0 2) and (1 0 2) omega-scan rocking curves are 119 and 202 arcsec, corresponding a high crystal quality. The status of the strain in ZnO thick film was particularly analyzed by X-ray diffraction (XRD) omega-20 scanning. The results show that the strain in ZnO film is compressive, which is also supported by Raman scattering spectroscopy. The compressive strain can solve the cracking problem in the quick growth of ZnO thick film. (c) 2008 Elsevier Ltd. All rights reserved.

Structural and optical properties of ZnO films on SrTiO3 substrates by MOCVD

ZnO films have been fabricated on (0 0 1), (0 1 1) and (1 1 1) SrTiO3 (STO) substrates by metal-organic chemical vapour deposition (MOCVD). It is interesting that the ZnO films on (0 0 1) and (0 1 1) STO substrates show polar and semipolar orientations, which are different from previous reports, while the same growing direction of polar ZnO with previous results is found on (1 1 1) STO. For the atomic arrangements, two orthogonal domains and a single domain are observed on (0 0 1) and (1 1 1) STO, respectively. Photoluminescence spectra show that every sample has a sharp near-band-edge emission peak at about 3.28 eV without any deep-level emission band between 1.5 and 2.8 eV, implying a high optical quality. A violet emission around 3.0 eV is observed only in ZnO films on (0 0 1) and (0 1 1) STO substrates grown at 600 degrees C, which is discussed briefly. Additionally, the semipolar ZnO does not weaken the emission efficiency along with the reduction in the polarization effect compared with polar ZnO. These results show that high-quality polar and semipolar ZnO films can be grown on STO substrates by MOCVD.

Low-temperature magnetotransport behaviors of heavily Mn-doped (Ga,Mn)As films with high ferromagnetic transition temperature

We report the low-temperature magnetotransport behaviors of (Ga,Mn)As films with the nominal Mn concentration x larger than 10%. The ferromagnetic transition temperature T-C can be enhanced to 191 K after postgrowth annealing (Ga,Mn)As with x=20%. The temperature T-m, corresponding to the resistivity minimum in the curve of resistivity versus temperature at temperature below T-C, depends on Mn concentration, annealing condition, and magnetic field. Moreover, we find that the variable-range hopping may be the main conductive mechanism when temperature is lower than T-m.

Design of shallow acceptors in ZnO through compensated donor-acceptor complexes: A density functional calculation

The intrinsic large electronegativity of O 2p character of the valence-band maximum (VBM) of ZnO renders it extremely difficult to be doped p type. We show from density functional calculation that such VBM characteristic can be altered by compensated donor-acceptor pairs, thus improve the p-type dopability. By incorporating (Ti+C) or (Zr+C) into ZnO simultaneously, a fully occupied impurity band that has the C 2p character is created above the VBM of host ZnO. Subsequent doping by N in ZnO: (Ti+C) and ZnO: (Zr+C) lead to the acceptor ionization energies of 0.18 and 0.13 eV, respectively, which is about 200 meV lower than it is in pure ZnO.

Photoluminescence characterization of nanocrystalline ZnO array

High-density and uniform well-aligned ZnO sub-micron rods are synthesized on the silicon substrate over a large area. The morphology, and structure of the ZnO sub-micron rods are investigated by x-ray diffraction, transmission electron microscopy and Raman spectra. It is found that the ZnO sub-micron rods are of high crystal quality with the diameter in the range of 400-600 nm and the length of several micrometres long. The optical properties were studied bill photoluminescence spectra. The results show that the intensity of the ultraviolet emission at 3.3 eV is rather high, meanwhile the deep level transition centred at about 2.38 eV is weak. The free exciton emission could also be observed at low, temperature, which implies the high optical quality of the ZnO sub-micron rods. This growth technique provides one effective way to fabricate the high crystal quality ZnO nanowires array, which is very important for potential applications in the new-type optoelectronic nanodevices.

Microstructural and compositional characteristics of GaN films grown on a ZnO-buffered Si(111) wafer

Polycrystalline GaN thin films have been deposited epitaxially on a ZnO-buffered (111)-oriented Si substrate by molecular beam epitaxy. The microstructural and compositional characteristics of the films were studied by analytical transmission electron microscopy (TEM). A SiO2 amorphous layer about 3.5 nm in thickness between the Si/ZnO interface has been identified by means of spatially resolved electron energy loss spectroscopy. Cross-sectional and plan-view TEM investigations reveal (GaN/ZnO/SiO2/Si) layers exhibiting definite a crystallographic relationship: [111](Si)//[111](ZnO)//[0001](GaN) along the epitaxy direction. GaN films are polycrystalline with nanoscale grains (similar to100 nm in size) grown along [0001] direction with about 20degrees between the (1 (1) over bar 00) planes of adjacent grains. A three-dimensional growth mode for the buffer layer and the film is proposed to explain the formation of the as-grown polycrystalline GaN films and the functionality of the buffer layer. (C) 2004 Elsevier Ltd. All rights reserved.

Nonradiative recombination centers in Ga(As,N) and their annealing behavior studied by Raman spectroscopy

Nitrogen-related defects in diluted Ga(As,N) have been detected by Raman scattering in resonance with the localized E+ transition. These defects are attributed to local vibrational modes of nitrogen dimers on Ga- and As-lattice sites. Rapid thermal annealing under appropriate conditions is found to be able to remove the nitrogen dimers. The required minimum annealing temperature coincides with the threshold-like onset of strong, near-band-gap photoluminescence. This finding suggests that the nitrogen dimers are connected with nonradiative recombination centers. (C) 2004 American Institute of Physics.

The magnetic and structure properties of room-temperature ferromagnetic semiconductor (Ga,Mn)N

Diluted magnetic semiconductor (Ga,Mn)N were prepared by the implantation of Mn ions into GaN/Al2O3 substrate. Clear X-ray diffraction peak from (Ga,Mn)N is observed. It indicates that the solid solution (Ga,Mn)N phase was formed with the same lattice structure as GaN and different lattice constant. Magnetic hysteresis-loops of the (Ga,Mn)N were obtained at room temperature (293 K) with the coercivity of about 2496.97 A m(-1). (C) 2003 Elsevier B.V. All rights reserved.