Structure and optical properties of Mg‐doped ZnO nanoparticles by polyacrylamide method

Mg‐doped ZnO (Mg_xZn_1‐xO) nanoparticles with precise stoichiometry are synthesized through polyacrylamide polymer method. Calcination of the polymer precursor at 650 °C gives particles of the homogeneous solid solution of the (Mg_xZn_1‐xO) system in the composition range (x < 0.15). ZnO doping with Mg causes shrinkage of lattice parameter c. The synthesized Mg_xZn_1‐xO nanoparticles are typically with the diameter of 70–85 nm. Blue shift of band gap with the Mg‐content is demonstrated, and photoluminescence (PL) from ZnO has been found to be tunable in a wide range from green to blue through Mg doping. The blue‐related PL therefore appeared to be caused by energetic shifts of the valence band and/or the conduction band of ZnO. Mg_xZn_1‐xO nanoparticles synthesized by polyacrylamide‐gel method after modified by polyethylene glycol surfactant have a remarkable improvement of stability in the ethanol solvent, indicating that these MZO nanoparticles could be considered as the candidate for the application of solution–processed technologies for optoelectronics at ambient temperature conditions.     

Grain boundary defects induced room temperature ferromagnetism in V doped ZnO thin films

Vanadium (V) doped ZnO thin films (Zn_1‐xV_x O, where x = 0, 0.05, 0.10) have been grown on sapphire substrates by RF magnetron sputtering to realize room temperature ferromagnetism (RTFM). The grown films have been subjected to X‐ray diffraction (XRD), resonant Raman scattering, photoluminescence (PL) and vibrating sample magnetometer (VSM) measurements to investigate their structural, optical and magnetic properties, respectively. The full width at half maximum of XRD and Raman scattering peaks increases with V ion concentration indicates that the V ions have been substituted on Zn²⁺ ions in the ZnO matrix. The increase in oxygen vacancies with V concentration is evidenced by PL measurements. Rutherford backscattering spectrometry analysis confirms the presence of the V ions in the films. The room temperature VSM measurements reveal the signature of ferromagnetism in V doped ZnO thin films. It has been observed that the grain boundary defects, i.e., oxygen vacancies play a crucial role in inducing RTFM in V doped ZnO films. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and electrical properties of Mg‐doped ZnO nanoparticles

Mg_xZn_1‐xO (x=0.01‐0.3) nanoparticles were synthesized by the sol‐gel technique using solutions of Mg and Zn based organometalic compounds. The electrical properties of Mg doped zinc oxide (ZnO) were studied within wide temperature range from 300 to 500 K under the N₂ gas flow (flow rate: 20 sccm) and in the frequency range from 40 Hz to 1 MHz for ac electrical measurements. The dc conductivities and the activation energies were found to be in the range of 10^‐9‐10^‐6 S/cm at the room temperature and 0.26‐0.86 eV respectively depending on doping rate of these samples. The ac conductivity was well represented by the power law Aω^s. The conduction mechanism for all doped ZnO could be related to correlated barrier hopping (CBH) model. The complex impedance plots (Nyquist plot) showed the data points lying on a single semicircle, implying the response originated from a single capacitive element corresponding to the nanoparticle grains. The crystal structures of the Mg_xZn_1‐xO nanoparticles were characterized using X‐ray diffraction. The calculated average particle sizes values of Zn_1‐xMg_xO samples are found between 29.72 and 22.43 nm using the Sherrer equation. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and magnetic studies of Mn‐doped ZnO

The bulk samples of Mn‐doped ZnO were synthesized with the nominal compositions Zn_1‐xMn_xO (x = 0.02, 0.05, 0.10, 0.15) by the solid‐state reaction and sol‐gel methods. In both the methods the samples were finally sintered at ∼700 °C in air. The X‐ray diffraction (XRD) studies of the samples synthesized by the solid‐state reaction method exhibit the presence of wurtzite (hexagonal) crystal structure similar to the parent compound (ZnO) in all the samples, suggesting that doped Mn ions sit at the regular Zn sites. However, same studies spread over the samples with Mn content ≥5% and synthesized by the sol‐gel method reveal the occurrence of some secondary phase in addition to the majority wurtzite phase. The magnetic measurements by vibrating sample magnetometer (VSM) clearly indicate ferromagnetic interaction at room temperature in all the samples. The Curie temperatures (T_c) and magnetization vary with concentration of Mn ions in the samples. However, the samples synthesized by sol‐gel method were found to have lower Tc values and also lower magnetization as compared to the corresponding samples synthesized by solid‐state reaction method. It could possibly be due to the presence of antiferromagnetic islands and smaller crystallite sizes in the samples prepared by sol‐gel method. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and morphological studies on Mn substituted ZnO nanometer‐sized crystals

Mn substituted ZnO nanocrystals synthesized by a co‐precipitation method. X‐ray diffraction (XRD) studies confirms the presence of wurtzite (hexagonal) crystal structure similar to un doped ZnO, suggesting that doped Mn ions go at the regular Zn sites. The lattice parameters a and c are increasing with increasing Mn content. The unit cell volume increases with increasing Mn concentration, indicating the homogeneous substitution of Mn²⁺ for the Zn²⁺. The lattice distortion parameter (ε_v) is evaluated from XRD data and found that it enhances as Mn content increases. Transmission electron microscopy photographs show that the size of the ZnO crystals is in the range of 20‐50 nm. The SAED pattern confirms the hexagonal and crystalline nature of the samples which are in agreement with X‐ray analysis. The chemical groups of the samples have been identified by FTIR studies (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Cr doping on the structural and optical properties of ZnS nanoparticles

Zn_1−xCr_x S nanoparticles with x = 0.00, 0.005, 0.01, 0.02 and 0.03 were synthesized by chemical co‐precipitation method at room temperature for the first time. Ethylene diamine tetraacetic acid was used as stabilizer. Energy dispersive analysis of X‐rays confirmed the presence of Cr in the samples. The samples were characterized by scanning electron microscopy, X‐ray diffraction (XRD), transmission electron microscopy and optical absorption studies. XRD and selected area electron diffraction results showed that the samples of all compositions crystallized in cubic structure and the lattice parameters decreased linearly with increase in Cr content following Vegard's law indicating that the Cr ions have substituted for Zn in the ZnS lattice. The particle size estimated from XRD was in the range 6–10 nm.The optical absorption studies on the doped samples indicated that the absorption edge blue shifted with respect to those of bulk and nanocrystalline ZnS. The bandgap increased with increasing Cr concentration in a narrow range 3.81–4.03 eV. Photolumonesence studies showed blue emission with appreciable luminescence quenching with increasing Cr concentration. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of rapid thermal annealing on Zn1‐xCdxO layers grown by radio‐frequency magnetron co‐sputtering

Zn_1‐xCd_xO layers were deposited on the sapphire substrate using the radio‐frequency magnetron co‐sputtering system. The grown Zn_1‐xCd_xO layers were carried out in the post‐annealing treatment for 1 min at the 800 °C oxygen‐ambient by the rapid thermal annealing (RTA) method. X‐ray diffraction (XRD) experiment shows that the Zn_1‐xCd_xO layers are changed from the single phase of the hexagonal structure at 0≤x ≤0.08 to the double phase of hexagonal‐and‐cubic structure at x =0.13. Thus, the maximum Cd‐composition ratio with the hexagonal structure was found out to be x =0.08. Also, the crystallinity of Zn_1‐xCd_xO layers at x =0.13 was remarkably improved by the RTA annealing treatment. This crystal quality improvement was thought to be associated with the relaxation of the compressive strain remaining in the Zn_1‐xCd_xO layers. Therefore, the results of XRD and transmittance lead that the crystal quality of the Zn_1‐xCd_xO layers forming the hexagonal ZnO phase is better than that forming the cubic CdO phase. Consequently, the reliable formation and the crystallinity of the Zn_1‐xCd_xO layers were achieved by using the RTA method of short‐time thermal‐annealing at the high temperature. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental and first‐principle investigation of Cu‐doped ZnO ferromagnetic powders

Zn_1‐xCu_x O powders were synthesized by using sol‐gel method. Electronic band structure and ferromagnetic properties of Zn_1‐xCu_x O powders were studied experimentally and theoretically. The simulations are based upon the Perdew‐Burke‐Ernzerhof form of generalized gradient approximation within the density functional theory. Zn_1‐xCu_x O shows dilute ferromagnetism, as a saturated magnetization of 0.9×10^‐3emu/g was observed for Zn_0.95Cu_0.05O powders. The strong p ‐d hybridization between Cu and its four neighbouring O atoms is responsible for the ferromagnetism. Comparing with ZnO whose Fermi level locates at the valence band maximum, the Fermi level of the Zn_1‐xCu_x O shifts upward into the valence band and hence the Zn_1‐xCu_x O system exhibits theoretically a p ‐type metallic semiconducting property. The Zn_1‐xCu_x O system may be a potential candidate in spintronics. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Paramagnetic behavior of Zn1−xMnxO at room temperature

Mn‐doped ZnO were synthesized by solid state reaction and sol‐gel method respectively. It was found that samples synthesized by solid state reaction containing Mn₂O₃ and MnO₂ are a mixture of ferromagnetic and paramagnetic phases. Contrary, samples without second phases were found to be paramagnetic at room temperature. According to previous report, interface effects between Zn‐rich Mn₂O₃ and MnO₂ interfaces may be the origin of the ferromagnetic behavior observed in our samples prepared by solid reaction, so the alloy of Zn_1−xMn_xO may be paramagnetic at room temperature. Prepared by sol‐gel technique, the samples without second phases in the XRD patterns are also room‐temperature paramagnetic. Therefore we believe that the magnetism of Zn_1−xMn_xO is paramagnetic at room temperature. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Zr‐doped CeO2 Hollow slightly‐truncated nano‐octahedrons: One‐pot synthesis,characterization and their application in catalysis of CO oxidation

Zirconium‐doped ceria hollow slightly‐truncated nano‐octahedrons (HTNOs) (Ce_1‐xZr_xO₂) were synthesized by a one‐pot, facile hydrothermal method. The morphology and crystalline structure were characterized with powder X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and the high resolution transmission electron microscopy (HRTEM). The composition and chemical valence on the surface of the as‐prepared Ce_1‐xZr_xO₂ powders were detected by X‐ray photoelectron spectroscopy (XPS) and energy dispersive spectrometry (EDS). The surface area and pore size distribution of as‐obtained Zr‐doped ceria HTNOs were measured by N₂ adsorption‐desorption measurement. Mechanisms for the growth of Zr‐doped ceria HTNOs are proposed as both oriented attachment and Ostwald ripening process and the formation of the hollow structure is strongly dependent on the addition of Zr⁴⁺ ions. Furthermore, the as‐obtained Zr‐doped ceria HTNOs revealed superior catalytic activity and thermal stability toward CO oxidation compared to pure ceria. It may provide a new path for the fabrication of inorganic hollow structures on introducing alien metal ions.     

Synthesis and characterization of simonkolleite nanodisks and their conversion into ZnO nanostructures

Simonkolleite (Zn₅(OH)₈Cl₂·2H₂O) nanodisks with a width of 40 nm have been successfully synthesized via a hydrothermal method using zinc chloride and ammonia as the starting materials. The conversion mechanisms from simonkolleite nanodisks to ZnO spindles under hydrothermal condition and to ZnO nanotablets under solid phase transformation were discussed respectively. The simonkolleite nanodisks obviously occur in hydrothermal system with the combination of a lower alkalinity, lower temperature (<363 K), a higher NH₄⁺ ions concentration and in existence of Cl^‐ anion. The morphologies, crystal phases and photoluminescence properties of as‐synthesized samples were investigated by field emission scanning electron microscopy, powder X‐ray diffractometer and fluorescence spectrophotometer. The photocatalytic activities of these as‐synthesized samples in the degradation of methyl orange have been demonstrated. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd–PSS films were processed using the acid of poly(styrene sulfonate) – H–PSS and neodymium nitrate – Nd(NO₃)₃; the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV–Vis–NIR spectral region presents typical electronic transitions of Nd³⁺ ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N–O groups in the range of 1400–720 cm^?1, prove the permanence of Nd(NO₃)_x, with x = 1, 2 and/or 3, in the H–PSS matrix. UV–Vis site selective photoluminescence data indicate that the incorporation of Nd³⁺ introduces a blue shift in PSS emission (325–800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd³⁺ reabsorption and energy transfer effects between the PSS matrix and Nd³⁺ were also observed. The IR emission of Nd–PSS films at 1076 nm (⁴F_3/2 → ⁴I_11/2) present constant efficiency, independent on Nd³⁺ concentration. The Judd–Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd³⁺. Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix.     

Structure and optical property of BexZn1‐xO nanorod arrays

Be_xZn_1‐xO nanorod arrays with high crystalline quality were fabricated on Si substrate by a simple, low‐cost hydrothermal method. The effect of Be‐corporation on the structure, morphology and optical property of ZnO nanorod arrays was investigated. The diameter of Be_xZn_1‐xO nanorods gradually decreased and the length of them increased with increasing Be concentration. Edge emissions of the Be_xZn_1‐xO nanorods show a obvious blue shift upon the increase of the Be content.     

Characterization of large‐sized Nd:YAG single crystals grown by horizontal directional solidification

Nd³⁺‐doped Y₃Al₅O₁₂ single crystals have been grown by the horizontal directional solidification (HDS) method in different thermal zone. The Grashof (G_r), Prandtl (P_r), Marangoni (M_a) and Rayleigh (R_a) numbers of melt in HDS system have been discussed for our experimental system to understand the mechanism of melt flow patterns and concentration gradient of dopant. The concentration gradient of Nd³⁺ ions was explained with melt flow processes during crystal growth in different thermal zone, and results indicated that high growth temperature will be helpful for uniformity of dopant in HDS‐grown single crystal. The main microscopic growth defects such as bubbles and irregular inclusions in HDS‐grown Nd:YAG crystals were observed, and the causes were discussed as well. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman investigation of ZnO and Zn1−xMnxO nanocrystals synthesized by precipitation method

Zn_1?xMn_xO nanocrystal samples have been successfully synthesized using the chemical precipitation method in aqueous solution. Comparing with pure ZnO NC, the Raman data recorded from the manganese-doped nanocrystals shows an enhancement of the peaks located at 334 and 439 cm^?1. Besides, a new feature at 659 cm^?1 emerges. X-ray diffraction (XRD) of the as-precipitated nanocrystal samples illustrates that Mn-doping only makes the XRD peaks of the as-precipitated Mn-doped nanocrystals shift towards lower angle values, but the crystal structure of bulk ZnO is still preserved in the Mn-doped samples. Hence, the high quality Zn_1?xMn_xO (x ? 0) nanocrystals are formed through the replacement of zinc ions by manganese ions.     

Predicting a major role of surface spins in the magnetic properties of ferrite nanoparticles

Room‐temperature magnetization hysterisis measurements were conducted on Mn_0.5Zn_0.5Gd_xFe_(2‐x)O₄ ferrite nanoparticles, with x = 0, 0.5, 1.0, 1.5. The structure of this ferrite is normal spinel where the added of Gd³⁺ ions occupied the octahedral sites and replaces Fe³⁺ ions. The saturation magnetization was found to increase with the initial addition of the Gd³⁺ ions followed by a sharp decrease with further addition of Gd³⁺ ions. The Curie temperature was found to increase up to Gd³⁺ concentration of x = 1.0, and then decreases at x = 1.5. These results were attributed to the surface spins. Because the size of Gd³⁺ ions is larger than that of Fe³⁺ ions, the substitution of Fe³⁺ ions with the Gd³⁺ ions results in surface disorder which results in surface spins. A core‐shell magnetization model was introduced where several factors were combined to explain our results. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth process and optical investigations of Nd:NaGd (MoO4)2 crystals with varying content of Nd and Gd

In this paper, [NaGd_1‐xNdx](MoO₄)₂ crystals with x = 0.005–0.05 were grown by Czochralski method at 950 ℃ for 10 hours and subsequently characterized by absorption spectroscopy and fluorescence spectroscopy. The intensity parameters of Nd³⁺ were calculated by Judd‐Ofelt theory, and the relationship between the parameters and Nd³⁺ concentration was analyzed. The results show that with the increasing Nd³⁺ concentration, the oscillator strength, stimulated emission cross‐section, Ω_t and spontaneous transition probability decrease slightly, while the fluorescence lifetime decreases significantly. However, the fluorescence branching ratio is almost unchanged with the increasing Nd³⁺concentration. The [NaGd_1‐xNd_x](MoO₄)₂ crystal with (x = 0.01) possesses the highest quantum efficiency of 88.98%, a good fluorescence line‐width of 23 nm, a large value of σ_em·τ_f up to 0.55 × 10⁻²² cm²·s and a stimulated emission cross‐section up to 3.747 × 10⁻¹⁹ cm² for the transition from ⁴F_3/2 to⁴I_11/2 at 1064 nm. Test results indicate that [NaGd_1‐xNd_x](MoO₄)₂ crystals are an excellent gain media for the solid state laser system.     

Co nanoclusters as origin of ferromagnetism in sol‐gel synthesized Zn1‐xCoxO (x = 0.05, 0.10 and 0.15) samples

We report on the structural and magnetic properties of the polycrystalline samples of Zn_1‐xCo_xO (x = 0.05, 0.10 and 0.15) synthesized via sol‐gel route. The air sintered samples of all compositions exhibit paramagnetic behaviour at room temperature, on the other hand the same samples on annealing in Ar/H₂ atmosphere show room temperature ferromagnetism (RTFM) with enhanced magnetization. The value of magnetization increases with the Co concentration (x) in both the air sintered and Ar/H₂ annealed samples. The observed ferromagnetism in the Ar/H₂ annealed Zn_1‐xCo_xO (x = 0.05, 0.10 and 0.15) samples is attributed to the presence of Co nanoclusters as detected by XRD and FESEM‐EDAX. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of Co‐doped ZnO films prepared by electrochemical deposition

We prepared Co‐doped ZnO films by the electrochemical deposition. X‐ray diffraction (XRD), high resolution transmission microscopy (HRTEM), x‐ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), x‐ray absorption near‐edge structure (XANES), vibrating sample magnetometer (VSM), optical absorption, and photoluminescence (PL) measurements were carried out on the samples. The results showed Co atoms substituted Zn atoms in the ZnO lattice without the formation of the impurity phase. VSM measurements showed the ferromagnetic properties for the Co‐doped ZnO samples. When the Co doping concentration increased, the band gaps were widened and the PL peak positions shifted towards the short wavelength direction. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Twin Structure of (La,Nd)GaO3 Solid Solutions

For La_1‐xNd_xGaO₃ crystals the La‐Nd substitution leads to decrease of spontaneous strains and for composition with x≈0.32 the six possible twin states of orthorhombic phase (m3mFmmm) may be degenerated in three twin states inhered in m3mF4/mmm species when a distorted perovskite pseudocell becomes tetragonal. The {110} and {112} reflection twins and axial twins with compositional planes close to (211) and (21‐1) (S‐walls) were identified in La_1‐xNd_xGaO₃ (x=0.07, 0.12, 0.20) solid solutions crystals. All observed twins are typical for crystals with GdFeO₃ type perovskite‐like structure. It has been shown that for x≤0.2 and x≥0.5 orientations of S‐walls weakly depend on La/Nd ratio, whereas in the range of 0.2<x<0.5 they depend strongly on the solid solution composition. The tilt angle between two twin states across twin boundary in La_1‐xNd_xGaO₃ (x<0.6) solid solutions is smaller than that between two twins in pure LaGaO₃ or NdGaO₃.