The effects of Zn vacancies on ferromagnetism in Cu-doped ZnO films controlled by oxygen pressure and Li doping

Zn0.99Cu0.01O films were studied experimentally and theoretically. The films were prepared by pulsed-laser deposition on Pt（111）/Ti/SiO2/Si substrates under various oxygen pressures to investigate the growth-dependence of the ferromagnetic properties. The structural, magnetic, and optical properties were studied, and it was found that all the samples possess a typical wurtzite structure, and that the films exhibit room-temperature ferromagnetism. The sample deposited at 600 ℃ and an oxygen pressure of 10 Pa showed a large saturation magnetization of 0.83 μB/Cu. The enhanced ferromagnetism in the （Cu, Li）-codoped ZnO is attributable to the existence of Zn vacancies （Vzn）, as shown by first-principles calcu- lations. The photoluminescence analysis demonstrated the existence of Vzn in both Zn0.99Cu0.01 O and （Cu, Li）-codoped ZnO thin films, and this plays an important role in the increase of ferromagnetism, according to the results of first-principles calculations.

Structural,optical,and electrical properties of Cu-doped ZrO_2 films prepared by magnetron co-sputtering

Copper （Cu）-doped ZrO2 （CZO） films with different Cu content （0 at.%- 8.07 at.%） are successfully deposited on Si （100） substrates by direct current （DC） and radio frequency （RF） magnetron co-sputtering. The influences of Cu content on structural, morphological, optical and electrical properties of CZO films are discussed in detail. The CZO films exhibit ZrO2 monocline （1^-11） preferred orientation, which indicates that Cu atoms are doped in ZrO2 host lattice. The crystallite size estimated form x-ray diffraction （XRD） increases by Cu doping, which accords with the result observed from the scanning electron microscope （SEM）. The electrical resistivity decreases from 2.63 Ω·cm to 1.48 Ω·cm with Cu doping content increasing, which indicates that the conductivity of CZO film is improved. However, the visible light transmittances decrease slightly by Cu doping and the optical band gap values decrease from 4.64 eV to 4.48 eV for CZO fihns.

Synthesis of Cu-Doped Mixed-Phase TiO_2 with the Assistance of Ionic Liquid by Atmospheric-Pressure Cold Plasma

An atmospheric-pressure dielectric barrier discharge （DBD） gas-liquid cold plasma was employed to synthesize Cu-doped TiO~ nanoparticles in an aqueous solution with the assistance of [C2MIM]BF4 ionic liquid （IL） and using air as the working gas. The influences of the discharge voltage, IL and the amount of copper nitrite were investigated. X-ray diffraction, N2 adsorption-desorption measurements and UV-Vis spectroscopy were adopted to characterize the samples. The results showed that the specific surface area of TiO2 was promoted with Cu-doping （from 57.6 m^2.g^-1 to 106.2 m^2.g^-1 with 3% Cu-doping）, and the content of anatase was increased. Besides, the band gap energy of TiO~ with Cu-doping decreased according to the UV-Vis spec- troscopy test. The 3%Cu-IL-TiO2 samples showed the highest eificiency in degrading methylene blue （MB） dye solutions under simulated sunlight with an apparent rate constant of 0.0223 min-1, which was 1.2 times higher than that of non-doped samples. According to the characterization results, the reasons for the high photocatalytic activity were discussed.

Studies of Photorefractive Crystals of Cu-Doped (K_(0.5) Na_(0.5))_(0.2)(Sr_(0.75)Ba_(0.25))_(0.9)Nb_2O_6

In this paper, photorefractive crystals of Cu-doped (K0.5Na0.5)0.2 (Sr0.75Ba0.25)0.9Nb2O6 (KNSBN) are systematically studied. A series of Cu-doped KNSBN crystals have been grown and the samples with Cu-dopant in different levels and thicknesses have been fabricated. Their photorefractive properties including two-wave coupling gain coefficients and response rate are experimentally studied in details. The results show that (1) with high Cudopant cocentration, the crystal has larger coupling gain coefficient, higher effective charge carrier density, and faster time response; (2) thinner sample shows larger coupling gain coefficientl (3) at shorter wavelength 9 the crystal sample shows larger coupling gain coefficient and faster time response. The Cu-doping mechanisms were briefly referred. The analyses of the relationships among the crystal’s two-wave coupling, absorption property and the self-pumped phase conjugation are given. All the results show that Cu-doped KNSBN crystals are a kind of very promising photorefractive materials.

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

Zn（1-x）Cux 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.

High Sensitivity of Porous Cu-Doped SnO2 Thin Films to Methanol

Porous Cu-doped SnO2 thin films were synthesized by the sol-gel dip-coating method for enhancing methanol sensing performance. The effect of Cu doping concentration on the SnO2 sensibility was investigated. XRD data confirm that the fabricated SnO2 films are polycrystalline with tetragonal rutile crystal structure. AFM and SEM micrographs confirmed the roughness and the porosity of SnO2 surface, respectively. UV-Vis spectrum shows that SnO2 thin films exhibit high transmittance in the visible region ~95%. The band gap (3.80 - 3.92 eV) and the optical thickness (893 - 131 nm) of prepared films were calculated from transmittance data. The sensing results demonstrate that SnO2 films have a high sensitivity and a fast response to methanol. In particular, 3% Cu-SnO2 films have a higher sensitivity (98%), faster response (10-2 s) and shorter recovery time (18 s) than other films.

The Impact of Nickel Source/Doping Elements/Buffer on the Structure of Ni(OH)_2

The nano-nickel hydroxide samples were prepared by means of ultrasonic-assisted precipitation and the impact of source/doping element/buffer on the structure of Ni（OH）： was studied. The results of XRD, IR and TEM testing clearly revealed that larger anionic radius of the nickel sources or the buffer solution was conducive to the formation of α-Ni（OH）2. The proportion of α-Ni（OH）： samples doped with two elements was larger than that doped with single element. Additionally, speciation, valence as well as the radius of doping ions can directly affect the phase of Ni（OH）2.

First-principles study of electronic and optical properties in wurtzite Zn_(1-x)Cu_xO

We perform a first-principles simulation to study the electronic and optical properties of wurtzite Zn1-xCuxO. The simulations are based upon the Perdew-Burke-Ernzerhof form of generalised gradient approximation within the density functional theory. Calculations are carried out in different concentrations. With increasing Cu concentration, the band gap of Znl-xCuxO decreases due to the shift of valence band. The imaginary part of the dielectric function indicates that the optical transition between O2p states in the highest valence band and Zn 4s states in the lowest conduction band shifts to the low energy range as the Cu concentration increases. Besides, it is shown that the insertion of Cu atom leads to redshift of the optical absorption edge. Meanwhile, the optical constants of pure ZnO and Zn0.75Cu0.250, such as loss function, refractive index and reflectivity, are discussed.

Ferromagnetism of Zn_(1-x)Cu_xO Polycrystalline Made by Solid State Reaction

The Zn1-xCuxO polycrystalline materials were prepared by doping CuO into wurtzite ZnO through solid state reaction. The high concentration of copper doping in ZnO exhibited remarkable room temperature ferromagnetism. The Experiments showed that the magnetization saturation rose with the increase of Cu content. For the low Cu content sample, the hysteresis loop was slightly tilted which indicated that the diamagnetism coexisted in this sample. The temperature dependence of magnetization of Zn1-xCuxO revealed that the magnetic exchange coupling depended on the doping concentration of Cu and there were many different local environments for magnetism. The measured hysteresis loop and temperature dependence of magnetization were overall performance of the magnetism coming from a wide distribution of ferromagnetic exchange couplings.

Photoluminescence and thermoluminescence properties of SnO_2 nanoparticles embedded in Li_2O-K_2O-B_2O_3 with Cu-doping

Cu-doped borate glass co-doped with SnO2nanoparticles is fabricated by melt quenching.The structure and morphology of the samples are examined by X-ray diffraction and field emission scanning electron microscopy.Up-conversion enhancement is observed in the photoluminescence（PL） and thermoluminescence（TL） intensities of the glass.PL emission spectra are identified in the blue and green regions,and a fourfold increase in emission intensity may be observed in the presence of embedded SnO2nanoparticles.The glow curve is recorded at 215 C,and fourfold increases in TL intensity are obtained by addition of 0.1 mol% SnO2nanoparticles to the glass.Higher TL responses of the samples are observed in the energy range of 15-100 KeV.At energy levels greater than;.1 MeV,however,flat responses are obtained.The activation energy and frequency factor of the second-order kinetic reaction are calculated by the peak shape method.

Copper and Nitrogen Co-Doping Effect on Visible-Light Responsive Photocatalysis of Plasma-Nitrided Copper-Doped Titanium Oxide Film

In order to clarify the visible-light responsive photocatalysis of TiO2 co-doped with Cu and N atoms, plasma-nitridation was taken place to Cu-doped TiO2 film. Cu-doped TiO2 films were prepared by dip-coating method and they were nitrided by nitrogen plasma in the plasma-enhanced CVD system. Cu-doped TiO2 films before and after plasma-nitridation show similar X-ray diffraction peaks of anatase TiO2. XPS analysis reveals that the ionic states of Ti and Cu in the Cu-doped TiO2 films are Ti4+ and Cu+, respectively. After nitrogen plasma treatment, oxygen atoms are released by substitution of nitrogen atoms in the TiO2 matrix, so that Cu+ is oxidized to generate Cu2+ and at the same time oxygen vacancy is formed. The absorption edge of both Cu-doped and plasma-nitrided Cu-doped TiO2 did red shift. Visible-light responsive photocatalytic activity of the Cu-doped TiO2 film degraded after nitrogen plasma treatment.

Co-Precipitation Synthesis and Characterization of Nanocrystalline Zinc Oxide Particles Doped with Cu²⁺Ions

Nanocrystalline Cu-doped ZnO particles were synthesized by the co-precipitation method. The composition, structural, optical and magnetic characterizations were performed by energy dispersive X-Ray spectroscopy, X-Ray diffraction, UV-Visible spectrometer, and vibrating sample magnetometer. The results confirmed that nanocrystalline Cu-doped ZnO particles have a hexagonal wurtzite structure with a high degree of crystallization and a crystallite size of 10 - 16 nm. For Cu above 11 at%, the X-Ray diffraction pattern possessed CuO secondary phase which shows the solubility limit of Cu in the ZnO lattice. Up to 11% at Cu, the presence of Cu in the ZnO lattice as Zn substitution indicated by an in- crease in lattice parameter values. Nanoparticles showed weak ferromagnetic characteristics at room temperature. The absence of secondary phase related to magnetic precipitate shown intrinsic ferromagnetic behaviour.

Insights into the mechanism of multiple Cu-doped Co Fe_(2)O_(4)nanocatalyst activated peroxymonosulfate for efficient degradation of Rhodamine B

The multiple metal catalyst as a promising nanomaterial has shown excellent activity in the peroxymonosulfate(PMS)activation for pollutant degradation.However,the role of special sites and in-depth understanding of the PMS activation mechanism are not fully studied.In this study,a Cu-doped CoFe_(2)O_(4)nanocatalyst(0.5CCF)was synthesized by a sol-gel and calcination method,and used for PMS activation to remove Rhodamine B(RhB).The results showed that the Cu doping obviously enhanced the catalytic performance of CoFe_(2)O_(4),with 99.70%of RhB removed by 0.5CCF while 74.91%in the CoFe_(2)O_(4)within 15 min.Based on the X-ray photoelectron spectroscopy and electrochemical analysis,this could be ascribed to the more low valence of Co and Fe species generated on the 0.5CCF and faster electron transfers occurred in the 0.5CCF due to the Cu doping.In addition,Cu doping could provide more reaction sites for the 0.5CCF to activate PMS for RhB removal.The metal species and the surface hydroxyl were the reaction sites of PMS activation,and the surface hydroxyl played an important role in surface-bound reactive species generation.During the PMS activation,the Cu not only activated PMS to produce reactive oxygen species(ROS),but also regenerated Co^(2+)and Fe^(2+)to accelerate the PMS activation.The non-radical of ^(1)O_(2)was the main ROS with a 99.35%of contribution rate,and the SO_(5)^(·–)self-reaction was its major source.This study provides a new insight to enhance the PMS activation performance of multiple metal catalysts by Cu doping in wastewater treatment.

Carbon hollow spheres as cocatalyst of Cu-doped TiO_(2)nanoparticles for improved photocatalytic H_(2)generation

The reasonable employment of cocatalyst in photocatalysis can effectively promote the photocatalytic H_(2)production activity.In this study,carbon hollow spheres(C),as a good conductive nonmetallic material,have been utilized as a novel cocatalyst and a matrix for loading the Cu-doped-TiO_(2)nanoparticles by a successive hydrother-mal method and metal molten salt method.The Cu-doped-TiO_(2)nanoparticles were tightly anchored on the surface of carbon hollow sphere to form a zero-dimensional/three dimensional(0D/3D)Cu-doped-TiO2/C heterojunction.The optimal Cu-doped-TiO_(2)/C heterojunction demon-strated greatly enhanced photocatalytic H_(2) generation activity(14.4 mmol·g^(-1)·h^(-1))compared with TiO_(2)(0.33 mmol·g^(-1)·h^(-1))and TiO_(2)/C(0.7 mmol·g^(-1)·h^(-1)).The performance improvement was mainly due to the syner-gistic effect of carbon hollow sphere cocatalyst and Cu-doping,the Cu-doping in TiO_(2)nanoparticles can minimize charge recombination and enhance the available photoex-cited electrons,while the 3D carbon hollow spheres can act as electron traps to accelerate the charge separation and offer abundant active sites for solar water splitting reaction.

Electrospun Cu-doped In_(2)O_(3) hollow nanofibers with enhanced H2S gas sensing performance

One-dimensional nanofibers can be transformed into hollow structures with larger specific surface area, which contributes to the enhancement of gas adsorption. We firstly fabricated Cu-doped In_(2)O_(3) (Cu-In_(2)O_(3)) hollow nanofibers by electrospinning and calcination for detecting H2S. The experimental results show that the Cu doping concentration besides the operating temperature, gas concentration, and relative humidity can greatly affect the H2S sensing performance of the In_(2)O_(3)-based sensors. In particular, the responses of 6%Cu-In_(2)O_(3) hollow nanofibers are 350.7 and 4201.5 to 50 and 100 ppm H2S at 250 ℃, which are over 20 and 140 times higher than those of pristine In_(2)O_(3) hollow nanofibers, respectively. Moreover, the corresponding sensor exhibits excellent selectivity and good reproducibility towards H2S, and the response of 6%Cu-In_(2)O_(3) is still 1.5 to 1 ppm H2S. Finally, the gas sensing mechanism of Cu-In_(2)O_(3) hollow nanofibers is thoroughly discussed, along with the assistance of first-principles calculations. Both the formation of hollow structure and Cu doping contribute to provide more active sites, and meanwhile a little CuO can form p–n heterojunctions with In_(2)O_(3) and react with H2S, resulting in significant improvement of gas sensing performance. The Cu-In_(2)O_(3) hollow nanofibers can be tailored for practical application to selectively detect H2S at lower concentrations.

Structural, optical and electron paramagnetic resonance studies on Cu-doped ZnO nanoparticles synthesized using a novel auto-combustion method

Nanocrystalline Zn1_xCuxO （x = 0, 0.02, 0.04, 0.06, 0.08） samples were synthesized by a novel auto-combustion method using glycine as the fuel material. The structural, optical and magnetic properties of the samples were characterized using XRD, SEM, photoluminescence （PL） and electron paramagnetic resonance （EPR） spectro- scopies. The XRD spectra of samples reveal the hexagonal wurtzite structures of ZnO. As the copper content increases, a diffraction peak at 28 = 39° corresponding to secondary phase of CuO （[111] crystalline face） appears when x≤ 6 mol.%. PL spectra of the samples show a strong ultraviolet （UV） emission and defect related visible emissions. Cu-doping in ZnO can effectively adjust the energy level in ZnO, which leads to red shift in the emission peak position in UV region. The EPR spectra of Cu-doped ZnO nanoparticles show a distinct and broad signal at room temperature, suggesting that it may be attributed to the exchange interactions within Cu2＋ ions.

Phosphoserine enhanced Cu-doped bioactive glass dynamic dual-network hydrogel for craniofacial bone defect repair

Flexible hydrogels containing various osteogenic inorganic constituents,which can accommodate complicated shape variations,are considered as ideal grafts for craniofacial bone defect reconstruction.However,in most hybrid hydrogels,poor interaction between the polymer network and particles has detrimental effects on hydrogel rheological and structural properties,clinical manipulation and repair efficacy.In this article,we designed and prepared a series of hyaluronic acid composite hydrogel containing Cu-doped bioactive glass(CuBG)and phosphoserine(PS),in which hyaluronic acid was modified by methacrylate groups and phenylboronic acid groups to form a double crosslinked network.PS acted as an interaction bridge of CuBG particles and HAMA-PBA network to improve the mechanical properties of the composite hydrogels.The CuBG/PS hydrogels exhibited suitable rheological properties(injectable,self-healing,shape-adaptable),bone tissue integrating ability and anti-bacterial property.Meanwhile,we found that CuBG and PS have synergistic effect on improving osteogenic efficiency both in vitro and in vivo,particularly when the ratio of CuBG to PS is lower than 3(9CB/3PS).This work provided a versatile and scalable approach to enhanced the interaction within inorganic particles and polymer network in hydrogels without extra modification on components.

Effects of Annealing Temperature on Cu-Doped ZnO Nanosheets

The synthesis of Cu-doped ZnO nanosheets at room temperature was reported in our previous paper. The effects of annealing temperature on Cu-doped ZnO nanosheets were studied in this paper. Cu-doped ZnO nanosheets were annealed at 200-500℃ in air. The annealed specimens were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. The results show that Cu concentration in Cu-doped ZnO nanosheets reduced with increasing annealing temperature. When annealing temperature was lower than Zn melting point （410℃）, the morphologies of the Cu-doped ZnO nanosheets remained nearly the same as that before annealing. However, when the annealing temperature was over Zn melting point, Cu-doped ZnO nanosheets changed to nanowires, wormlike nanosheets or did not change. The change of Cu concentration in Cu-doped ZnO nanosheets is explained by oxidation thermodynamics. A physical model is suggested to explain the morphology changes of Cu-doped ZnO nanosheets, based on the existence of Cu-rich layer beneath Cu-doped ZnO nanosheets.

Highly efficient two-electron electroreduction of oxygen into hydrogen peroxide over Cu-doped TiO_(2)

Electrosynthesis of hydrogen peroxide(H2O_(2)),as a sustainable alternative to the anthraquinone oxidation method,provides the feasibility of directly generating H_(2)O_(2).Here,we report Cu-doped TiO_(2) as an efficient electrocatalyst which exhibits the excellent two-electron oxygen reduction reaction(2e-ORR)performance with respect to the pristine TiO_(2).The Cu doping results in the distortion of TiO_(2) lattice and further forms a large number of oxygen vacancies and Ti^(3+).Such Cu-doped TiO_(2) exhibits a positive onset potential about 0.79 V and high H_(2)O_(2) selectivity about 91.2%.Moreover,it also shows a larger H_(2)O_(2) yield and good stability.Density functional theory(DFT)calculations reveal that Cu dopant not only improves the electrical conductivity of pristine TiO_(2) but reduces the*OOH adsorption energy of active sites,which is beneficial to promote subsequently 2e-ORR process.

First-Principles Studies for Magnetism in Cu-Doped GaN

Hole carrier mediated magnetization in Cu-doped GaN is investigated by using the first-principles calculations. By studying the sp-d interaction and the direct exchange interaction among the dopants, we obtain an equation to determine the spontaneous magnetization as a function of the Cu dopant concentration and the hole carrier density. It is demonstrated that nonmagnetic Cu doped GaN can be of room-temperature ferromagnetism. The system＇s Curie temperature Tc can reach about 345 K with Cu concentration of 1.0% and hole carrier density of 5.0×10^19 cm-3. The results are in good agreement with experimental observations and indicate that ferromagnetism in this systems is tunable by controlling the Cu concentration and the hole carrier density.