Raman scattering investigations on Co-doped ZnO epitaxial films: Local vibration modes and defect associated ferromagnetism

Raman scattering spectroscopy has been performed on high quality Co-doped ZnO epitaxial films, which were grown on Al₂O₃ (0001) by oxygen-plasma assisted molecular beam epitaxy. Raman measurements revealed two local vibration modes (LVMs) at 723 and 699 cm⁻¹ due to the substitution of Co²⁺ in wurtzite ZnO lattice. The LVM at 723 cm⁻¹ is found to be an elemental sensitive vibration mode for Co substitution. The LVM at 699 cm⁻¹ can be attributed to enrichment of Co²⁺ bound with oxygen vacancy, the cobalt–oxygen vacancy–cobalt complexes, in Zn_1−xCo_xO films associated with ferromagnetism. The intensity of LVM at 699 cm⁻¹, as well as saturated magnetization, enhanced after the vacuum annealing and depressed after oxygen annealing.     

Structural,optical and magnetic properties of Cu and V co-doped ZnO nanoparticles

Zn_0.98−xCu_xV_0.02O (x=0, 0.01, 0.02 and 0.03) samples were synthesized by the sol–gel technology to dope up to 3% Cu in ZnO. Investigations of structural, optical and magnetic properties of the samples have been done. The results of X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) indicated that the V and Cu ions were incorporated into the crystal lattices of ZnO. With Cu doping concentration increasing up to 2 at%, the XRD results showed that all diffraction peaks corresponded to the wurtzite structure of ZnO. Photoluminescence (PL) measurements showed that Zn_0.98−xCu_xV_0.02O powders exhibited that the position of the ultraviolet (UV) emission peak of the samples showed an obvious red-shift and the green emission peak enhanced significantly with Cu doping in ZnVO nanoparticle. Magnetic measurements indicated that room temperature ferromagnetism (RTFM) of Zn_0.98−xCu_xV_0.02O was an intrinsic property when Cu concentration was less than 3 at%. The saturation magnetization (M_s) of Zn_0.98−xCu_xV_0.02O (x=0, 0.01 and 0.02) increased with the increase of the Cu concentration.     

Effect of Ce and Cu co-doping on the structural,morphological, and optical properties of ZnO nanocrystals and first principle investigation of their stability and magnetic properties

Ce, Cu co-doped ZnO (Zn_1−2xCe_xCu_xO: x=0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) nanocrystals were synthesized by a microwave combustion method. These nanocrystals were investigated by using X-ray diffraction (XRD), UV–visible diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM). The stability and magnetic properties of Ce and Cu co-doped ZnO were probed by first principle calculations. XRD results revealed that all the compositions are single crystalline. hexagonal wurtzite structure. The optical band gap of pure ZnO was found to be 3.22 eV, and it decreased from 3.15 to 3.10 eV with an increase in the concentration of Cu and Ce content. The morphologies of Ce and Cu co-doped ZnO samples confirmed the formation of nanocrystals with an average grain size ranging from 70 to 150 nm. The magnetization measurement results affirmed the antiferro and ferromagnetic state for Ce and Cu co-doped ZnO samples and this is in agreement with the first principles theoretical calculations.     

Influences of Al doping concentration on structural,electrical and optical properties of Zn0.95Ni0.05O powders

Nanocrystalline Zn_0.95−xNi_0.05Al_xO (x = 0.01, 0.02, 0.05 and 0.10) diluted magnetic semiconductors have been synthesized by an auto-combustion method. X-ray diffraction measurements indicate that all Al-doped Zn_0.95Ni_0.05O samples have the pure wurtzite structure. Transmission electron microscope analyses show that the as-synthesized powders are of the size 40–45 nm. High-resolution transmission electron microscope, energy dispersive spectrometer and X-ray photoemission spectroscope analyses indicate that Ni²⁺ and Al³⁺ uniformly substitute Zn²⁺ in the wurtzite structure without forming any secondary phases. The Al doping concentration dependences of cell parameters (a and c), resistance and the ratio of green emission to UV emission have the similar trends.     

Influence of Cu doping on the microstructure,optical properties and photoluminescence features of Cd0.9Zn0.1S nanoparticles

Cd_0.9−xZn_0.1Cu_xS (0≤x≤0.06) nanoparticles were successfully synthesized by a conventional chemical co-precipitation method at room temperature. Crystalline phases and optical absorption of the nanoparticles have been studied by X-ray diffraction (XRD) and UV–visible spectrophotometer. XRD confirms the phase singularity of the synthesized material, which also confirmed the formation of Cd–Zn–Cu–S alloy nanocrystals rather than separate nucleation or phase formation. Elemental composition was examined by the energy dispersive X-ray analysis and the microstructure was examined by scanning electron microscope. The blue shift of absorption edge below Cu=2% is responsible for dominance of Cu⁺ while at higher Cu concentration dominated Cu²⁺, d–d transition may exist. It is suggested that the addition of third metal ion (Cu²⁺/Cu⁺) is an effective way to improve the optical property and stability of the Cd_0.9Zn_0.1S solid solutions. When Cu is introduced, stretching of Cd–Zn–Cu–S bond is shifted lower wave number side from 678 cm⁻¹ (Cu=0%) to 671 cm⁻¹ (Cu=6%) due to the presence of Cu in Cd–Zn–S lattice and also the size effect. The variation in blue band emission peak from 456 nm (∼2.72 eV) to 482 nm (∼2.58 eV) by Cu-doping is corresponding to the inter-band radiation combination of photo-generated electrons and holes. Intensity of red band emission centered at 656 nm significantly increased up to Cu=4%; beyond 4% it is decreased due to the quenching of Cu concentration.     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

Tailoring Cu2−xTe quantum-dot-decorated ZnO nanoparticles for potential solar cell applications

Cu_2−xTe QDs on ZnO nanoparticles were synthesized using a successive ionic layer absorption and reaction technique (SILAR) at room temperature. The as-synthesized QDs which were distributively deposited on ZnO nanoparticles surface were characterized by field emission scanning electron microscope (FE-SEM), X-ray diffraction and high-resolution transmittance microscope (HR-TEM). It revealed that the average diameter of the QDs was ∼2 nm. The synthesized Cu_2−xTe QDs were solely orthorhombic Cu_1.44Te phase. The growth mechanism was supposed that it based on ions deposition. The energy gap of as-synthesized Cu_2−xTe QDs was determined ∼1.1 eV and the smallest energy gap of 0.76 eV was obtained, equal to that of bulk material. Raman spectroscopy and FTIR were also used to study the Cu_2−xTe QDs on ZnO nanoparticles. These characteristics suggest a promising implication for a potential broadband sensitizer of QDSCs.     

Raman spectroscopy of Cu doping in Zn1−xCoxO diluted magnetic semiconductor

The room‐temperature ferromagnetism and the Raman spectroscopy of the Cu‐doped Zn_1−xCo_xO powders prepared by the sol–gel method are reported. The x‐ray diffraction (XRD) data confirmed that the wurtzite structure of ZnO is maintained for ZnO doped with Co below 10 at%. The magnetization–field curves measured at room temperature demonstrated that all Co‐doped ZnO powders were paramagnetic. Ferromagnetic ordering is observed for the samples doped with Cu in Zn_0.98Co_0.02O and strongly depends on the concentration of Cu. The relative strength of the second‐order LO peak to the first‐order one in the Raman spectra, which is related to the carrier concentration, of the Cu‐doped Zn_0.98Co_0.02O powder is strongly correlated with the saturation magnetic moment of the system. This seems to be in favor of the Ruderman‐Kittel‐Kasuya‐Yosida (RKKY) or double exchange mechanism of the ferromagnetism in this system. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of Cd concentration on structure and optical properties of the ternary Zn1−xCdxO nanopowder prepared by sol–gel method

Zn_1−xCd_xO nanocrystalline powder with different Cd contents (0≤x≤1) has been prepared by new facile sol–gel route. The crystal structure and optical properties were investigated by X-ray diffraction patterns, Transmission electron microscope, X-ray photoelectron spectroscopy, Photoluminescence. As x varied from x=0 to 0.25, the Zn_1−xCd_xO nanopowder exhibits a hexagonal wurtzite structure of pure ZnO without any significant formation of a separated CdO phase. For the samples with 0.5≤x≤0.85, the Zn_1−xCd_xO nanopowder exhibits the coexistence of hexagonal ZnO and cubic CdO phase, meanwhile, the content of ZnO phase decreases while that of CdO increases with increasing the Cd content x. The ultra-violet near-band-edge emission of the Zn_1−xCd_xO nanopowder was monotonously red-shifted from 389 nm (x=0) to 406 nm (x=0.25) due to the direct modulation of band gap caused by Cd substitution.     

Micro Raman,Mossbauer and magnetic studies of manganese substituted zinc ferrite nanoparticles: Role of Mn

A series of Mn–Zn Ferrite nanoparticles (<15 nm) with formula Mn_xZn_1−xFe₂O₄ (where x=0.00, 0.35, 0.50, 0.65) were successfully prepared by citrate-gel method at low temperature (400 °C). X-ray diffraction analysis confirmed the formation of single cubic spinel phase in these nanoparticles. The FESEM and TEM micrographs revealed the nanoparticles to be nearly spherical in shape and of fairly uniform size. The fractions of Mn²⁺, Zn²⁺ and Fe³⁺ cations occupying tetrahedral sites along with Fe occupying octahedral sites within the unit cell of different ferrite samples are estimated by room temperature micro-Raman spectroscopy. Low temperature Mossbauer measurement on Mn_0.5Zn_0.5Fe₂O₄ has reconfirmed the mixed spinel phase of these nanoparticles. Room temperature magnetization studies (PPMS) of Mn substituted samples showed superparamagnetic behavior. Manganese substitution for Zn in the ferrite caused the magnetization to increase from 04 to18 emu/g and Lande's g factor (estimated from ferromagnetic resonance measurement) from 2.02 to 2.12 when x was increased up to 0.50. The FMR has shown that higher Mn cationic substitution leads to increase in dipolar interaction and decrease in super exchange interaction. Thermomagnetic (M–T) and magnetization (M–H) measurements have shown that the increase in Mn concentration (up to x=0.50) enhances the spin ordering temperature up to 150 K (blocking temperature). Magnetocrystalline anisotropy in the nanoparticles was established by Mossbauer, ferromagnetic resonance and thermomagnetic measurements. The optimized substitution of manganese for zinc improves the magnetic properties and makes these nanoparticles a potential candidate for their applications in microwave region and biomedical field.     

A study on the Raman spectra of Al-doped and Ga-doped ZnO ceramics

Al_xZn_1−xO and Ga_yZn_1−yO ceramics were synthesized through a solid-state reaction technique. The crystal phase of the samples was identified by an X-ray diffraction experiment. For each sample, the electrical resistivity was determined. The Al 2-mol%-doped and Ga 0.5-mol%-doped ZnO ceramics had the lowest resistivity. Raman measurement was performed to study the doping effects in the ZnO ceramics including ZnO single crystal as a reference. The line-shape parameters, q₁ and Γ₁, at the same certain doping rate and the solubility limit of Al (2 mol%) and Ga (0.5 mol%) in ZnO ceramics, are strongly related to the each other, and that the solubility limit plays an important role. The second-order Raman peak at 1162 cm⁻¹ of the ZnO ceramics was fitted by Fano formalism. The Fano’s fitting parameters, such as the lifetime of phonon and the degree of asymmetry degree of the second-order Raman peak changed as the amounts of dopants were varied.     

Low‐temperature synthesis and Raman scattering of Mn‐doped ZnO nanopowders

Nanocrystalline Mn‐doped zinc oxides Zn_1−xMn_xO (x = 0–0.10) were synthesized by the sol–gel technique at low temperature. The calcination temperature of the as‐prepared powder was found at 350 °C using differential thermal analysis. A thermogravimetric analysis showed that there is a mass loss in the as‐prepared powder till 350 °C and an almost constant mass till 800 °C. The X‐ray diffraction patterns of investigated nanopowders calcined at 350 °C correspond to the hexagonal ZnO structure without any foreign impurities. The average grain size of the nanocrystal that was observed around ∼25–40 nm from transmission electron microscopy matched well with the crystallite size calculated from the line shape of X‐ray diffraction. The chemical bonding structure in Zn_1−xMn_xO nanopowders was examined using X‐ray photoelectron spectroscopy techniques, which indicate substitution of Mn²⁺ ions into Zn²⁺ sites in ZnO lattice. Micro Raman spectroscopy confirmed the insertion of Mn ions in the ZnO host matrix, and similar wurtzite structure of Zn_1−xMn_xO (x < 10%) nanocrystals. Temperature‐dependent Raman spectra of the nanocrystals displayed suppression of luminescence and enhancement in full width at half maximum in pure ZnO nanocrystals with increase in temperature, which suggests an enhancement in particle size at elevated temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Characteristics of pulse plated CdxZn1−xSe films

Cd_xZn_1−xSe films (0 ⩽ x ⩽ 1) were deposited for the first time by the pulse plating technique at different duty cycles in the range 6–50% at room temperature from an aqueous bath containing zinc sulphate, cadmium sulphate and selenium oxide. To the author’s knowledge this is the first report on pulse plated Cd_xZn_1−xSe films. The deposition potential was −0.9 V (SCE). The as deposited films exhibited cubic structure. Composition of the films was estimated by Energy Dispersive Analysis of X-ray studies. X-ray photoelectron spectroscopy studies indicated the binding energies corresponding to Zn(2p_3/2), Cd(3d_5/2 and 3d_3/2) and Se(3d_5/2 and 3d_3/2). Optical band gap of the films varied from 1.72 to 2.70 eV as the composition varied from CdSe to ZnSe side. Atomic force microscopy studies indicated grain size in the range of 20–150 nm.     

Magnetic and Raman scattering studies of Co-doped ZnO thin films grown by pulsed laser deposition

Phase pure Zn_1?x Co _x O thin films grown by pulsed laser deposition have transmittance greater than 75 % in the visible region. Raman studies confirm the crystalline nature of Zn_1?x Co _x O thin films. Zn_0.95Co_0.05O thin films show room temperature ferromagnetism with saturation magnetization of 0.4μ _B /Co atom. The possible origin of paramagnetism at higher Co doping concentrations can be attributed to the increased nearest-neighbor antiferromagnetic interactions between Co²⁺ ions in ZnO matrix. XPS confirms the substitution of Co²⁺ ions into the ZnO host lattice.     

Structure and ferromagnetic properties of Co-doped ZnO powders

Single-phase Zn_1−xCo_xO (x=0.02, 0.04) powders were synthesized by a simple co-precipitation technique. X-ray diffraction analysis reveals that the Co-doped ZnO crystallizes in a wurtzite structure. The lattice constants of Co-doped ZnO powders decrease slightly when Co is doped into ZnO. Optical absorption spectra show a decrease in the bandgap with increasing Co content and also give an evidence of the presence of Co²⁺ ions in tetrahedral sites. Raman spectra indicate that Co doping increased the lattice defects and induced another Raman vibration mode around at 538 cm⁻¹, which is an indicator for the incorporation of Co²⁺ ions into the ZnO host matrix. Magnetic measurement reveals that the Zn_1−xCo_xO (x=0.02, 0.04) powders clearly exhibit room-temperature ferromagnetic behavior, which makes them potentially useful as building components for spintronics.     

Structural and magnetic studies on Zr doped ZnO diluted magnetic semiconductor

In this study, Zirconium doped Zn_1−xZr_xO (with x = 0.00–0.10) samples have been prepared by formal solid-state reaction technique. The Zr doped ZnO samples annealed at 1100 °C and characterized by different characterization techniques, such as X-ray diffraction (XRD), Scanning electron microscope (SEM), Vibrating sample magnetometer (VSM) and Fourier transform infrared spectroscopy (FTIR). The X-ray diffraction (XRD) used to study the structural properties. XRD pattern showed that lattice parameters, “a”, “c”, unit cell volume and Zn–O bond length increase with doping content (x ≤ 0.04) where as these decrease with x > 0.04. On the other hand, reverse trend observed with lattice distortion. The crystallite size decreases with increasing doping content of Zr. FTIR employed to investigate functional chemical bonding properties of different elements and compounds present in materials. The low, medium and high frequency absorption bands observed at 630, 1500 and 3435 cm⁻¹, which were the common features of Zn–O, H–O–H and O–H bond respectively. SEM used to study surface morphology and measured grain size of specimen. The surface becomes dense and grain size decreases with increasing degree of Zr contents. The SEM micrograph also shows the presence of spherical micro size particles and formation of pores in samples. Magnetic properties were obtained using VSM. The samples exhibit room temperature ferromagnetism. The magnetic hysteresis loops show variation in the value of magnetic parameter. The saturation magnetization (M_s) and coercivity (H_c) decrease, while remanence magnetization (M_r) shows gradually increasing trend with Zr content. VSM measurement reveals that sample Zn_0.96Zr_0.4O show better result as compared to x = 0.06–0.10.     

Optical and structural properties of Zn1−x Mg x O ceramic materials

This paper reports structural, optical and cathodoluminescence characterizations of sintered Zn_1?x Mg _x O composite materials. The effects of MgO composition on these film properties have been analyzed. X-ray diffraction (XRD) confirms that all composites are polycrystalline with prominent hexagonal wurtzite structure along two preferred orientations (002) and (101) for the crystallite growth. Above doping content x = 10 %, the formation of the hexagonal ZnMgO alloy phase and the segregation of the cubic MgO phase start. From reflectance and absorption measurements, we determined the band gap energy which tends to increase from 3.287 to 3.827 eV as the doping content increases. This widening of the optical band gap is explained by the Burstein–Moss effect which causes a significant increase of electron concentration (2.89 × 10¹⁸?5.19 × 10²⁰ cm^?3). The luminescent properties of the Zn_1?x Mg _x O pellets are studied by cathodoluminescence (CL) at room and liquid nitrogen temperatures under different electron beam excitations. At room temperature, the CL spectra of the Zn_1?x Mg _x O composites exhibit a dominant broad yellow-green light band at 2.38 eV and two ultraviolet emission peaks at 3.24 and 3.45 eV corresponding to the luminescence of the hexagonal ZnO and ZnMgO structures, respectively. For the doped ZnO samples, it reveals also new red peaks at 1.72 and 1.77 eV assigned to impurities’ emissions. However, the CL spectra recorded at 77 K show the presence of excitonic emission peaks related to recombination of free exciton (X _A), neutral donor-bound excitons (D⁰X) and their phonon replicas. The CL intensity and energy position of the green, red and ultraviolet emission peaks are found to depend strongly on the MgO doping content. The CL intensity of the UV and red emissions is more enhanced than the green light when the MgO content increases. CL imaging analysis shows that the repartition of the emitting centers in Zn_1?x Mg _x O composites is intimately connected to the film composition and surface morphology.     

On the structural,optical and electrical properties of Cu2+ doped Zn0.94Cd0.06O nanomaterials

Nanoparticles of Cu²⁺ doped Zn_0.94Cd_0.06O oxide with formula Zn_0.94Cd_0.06-xCu_xO [x = 0.0, 0.03, 0.05] were prepared via sol-gel auto combustion (SGAC) method at pH value of 10. Room temperature X-ray powder diffraction (XRD) patterns confirms that all the synthesized samples were single-phased polycrystalline with wurtzite hexagonal structure (P6₃mc). Crystallite size is estimated from XRD which was found to be 29–40 nm. Using Rietveld refinement of XRD data, the structure, space group and other structure related parameters were confirmed. The nanoparticle formation was confirmed via field emission scanning electron microscopy (FE-SEM) and elemental composition was verified through energy dispersive analysis of X-rays (EDAX). Raman spectroscopy reveals seven active phonon modes for both pristine Zn_0.94Cd_0.06O and Zn_0.94Cd_0.06-xCu_xO [x = 0.03, 0.05]. The oxide formation is also conveyed through Fourier transformation of Infra-red (FTIR) spectroscopy. The bandgap using UV–Vis spectroscopy was found to be about 3.02 eV and 3.09 eV for Zn_0.94Cd_0.06-xCu_xO (x = 0.03, 0.05), 3.14 eV for pristine Zn_0.96Cd_0.06O. The dielectric studies confirmed high dielectric constant for Zn_0.94Cd_0.06O that decreases gradually on increasing Cu²⁺ doping concentration. The impedance analysis of all samples shows non-Debye character with spread of relaxation times.     

Theoretical investigation of electronic structure and optical response in relation to the transport properties of Ga1−xInxN (x = 0, 0.25, 0.50, 0.75)

The state-of-the-art all-electron FLPAW method and the BoltzTrap software package based on semi-classical theory were adopted to explore the electronic structure and the optical and thermoelectric properties of Ga_1−xIn_xN. Ga_1−xIn_xN is predicted to be a direct band gap material for all values of x. Moreover, the band gap varies between 2.99 eV and 1.95 eV as x changes. Optical parameters such as the dielectric constant, absorption coefficient, reflectivity and refractive index are calculated and discussed in detail. The doping of In plays an important role in the modulation of the optical constants. The static dielectric constant ɛ(0) of Ga_1−xIn_xN was calculated as 3.95, 3.99, 3.99 and 4.03 at x = 0.00, 0.25, 0.50 and 0.75, respectively. The static refractive index is 2.0 for pure Ga_1−xIn_xN at x = 0.00. The thermal properties varied greatly as x fluctuated. The ternary alloy has large values for the Seebeck coefficient and figure of merit at high temperatures and is thus suitable for thermoelectric applications. Pure Ga_1−xIn_xN at x = 0 exhibited ZT = 0.80 at room temperature, and at higher temperatures, the thermal conductivity decreased with increased In doping.     

Room temperature ferromagnetism in Ni-doped ZnO films

Zn_1−xNi_xO (x = 0.02, 0.03, 0.04, 0.05, 0.07) films were prepared using magnetron sputtering. X-ray diffraction indicates that all samples have a wurtzite structure with c-axis orientation. X-ray photoelectron spectroscopy results reveal that the Ni ion is in a +2 charge state in these films. Magnetization measurements indicate that all samples have room temperature ferromagnetism. In order to elucidate the origin of the ferromagnetism, Zn_0.97Ni_0.03O films were grown under different atmospheric ratios of argon to oxygen. The results show that as the fraction of oxygen in the atmosphere decreases, both the saturation magnetization and the number of oxygen vacancies increase, confirming that the ferromagnetism is correlated with the oxygen vacancy level.