Effects of doping concentration on properties of Mn-doped ZnO thin films

This paper reports that the radio frequency magnetron sputtering is used to fabricate ZnO and Mn-doped ZnO thin films on glass substrates at 500 ℃. The Mn-doped ZnO thin films present wurtzite structure of ZnO and have a smoother surface, better conductivity but no ferromagnetism. The x-ray photoelectron spectroscopy results show that the binding energy of Mn2p3/2 increases with increasing Mn content slightly, and the state of Mn in the Mn-doped ZnO thin films is divalent. The chemisorbed oxygen in the Mn-doped ZnO thin films increases with increasing Mn doping concentration. The photoluminescence spectra of ZnO and Mmdoped ZnO thin films have a similar ultraviolet emission. The yellow green emissions of 4 wt.% and 10 wt.% Mn-doped thin films are quenched, whereas the yellow green emission occurs because of abundant oxygen vacancies in the Mn-doped ZnO thin films after 20 wt.% Mn doping. Compared with pure ZnO thin film, the bandgap of the Mn-doped ZnO thin films increases with increasing Mn content.

Synthesis of high-TC ferromagnetic Mn-doped ZnO nanorods by thermal evaporation

This paper reports that a large amount of Mn-doped ZnO nanorods have been synthesized through thermal evaporation. The morphologies and properties are studied with x-ray diffraction, a scanning electron microscope, transmission electron microscope and Raman spectroscope. The results indicate that the manganese atoms occupy the zinc vacancies in the wurtzite lattice of ZnO without forming secondary phases. The exact manganese content has been studied by the x-ray fluorescence spectrum. Meanwhile, the magnetic moment versus temperature result proves that the as-prepared Mn-doped ZnO nanorods show ferromagnetic properties at temperatures as high as 400~K. These studies provide a good understanding of the origin of magnetic properties in diluted magnetic semiconductors.

Magnetic properties of Mn-doped ZnO diluted magnetic semiconductors

A series of Mn-doped ZnO films have been prepared in different sputtering plasmas by using the inductively coupled plasma enhanced physical vapour deposition. The films show paramagnetic behaviour when they are deposited in an argon plasma. The Hall measurement indicates that ferromagnetism cannot be realized by increasing the electron concentration. However, the room-temperature ferromagnetism is obtained when the films are deposited in a mixed argon-nitrogen plasma. The first-principles calculations reveal that antiferromagnetic ordering is favoured in the case of the substitution of Mn^2＋ for Zn^2＋ without additional acceptor doping. The substitution of N for O （NO^-） is necessary to induce ferromagnetic couplings in the Zn-Mn-O system. The hybridization between N 2p and Mn 3d provides an empty orbit around the Fermi level. The hopping of Mn 3d electrons through the empty orbit can induce the ferromagnetic coupling. The ferromagnetism in the N-doped Zn-Mn-O system possibly originates from the charge transfer between Mn^2＋ and Mn^3＋ via NO^-, The key factor is the empty orbit provided by substituting N for O, rather than the conductivity type or the carrier concentration.

Optical properties of ZnO and Mn-doped ZnO nanocrystals by vapor phase transport processes

In this paper we investigated the optical properties of ZnO and Mn doped ZnO nanocrystals that were fabricated by a vapor phase transport growth process, using zinc acetate dihydrate with or without Mn in a constant O2/Ar mixture gas flowing through the furnace at 400600℃, respectively. The as grown ZnO nanocrystals are homogeneous with a mean size of 19 nm observed by scanning electron microscope（SEM）. The optical characteristics were analyzed by absorption spectra and photoluminescence（PL） spectra at room-temperature. For ZnO nanocrystals, a strong and predominant UV emission peaked at 377 nm was found in the PL spectra. For Mn doped ZnO nanocrystals, in addition to the strong UV emission, a strong blue emission peaked at 435 nm was observed as well. By doping Mn ions, the major UV emission shifts from 377 nm to 408 nm, showing that Mn ions were not only incorporated into ZnO Ncs, but also introduced an impurity level in the bandgap. Moreover, with the concentration of Mn increasing, the relative intensities of the two emissions change largely, and the photoluminescence mechanism of them is discussed.

Bifunctional Mn-doped CoSe_(2) nanonetworks electrode for hybrid alkali/acid electrolytic H_(2) generation and glycerol upgrading

Electrolytic water splitting,as a promising route to hydrogen(H_(2))production,is still confronted with the sluggish anodic oxygen evolution reaction(OER)and its less value-added O2 production.Herein,we report a bifunctional electrode fabricated by in situ growth of Mn-doped CoSe_(2)nanonetworks on carbon fiber cloth(Mn-CoSe_(2)/CFC),which shows attractive electrocatalytic properties toward glycerol oxidation reaction(GOR)in alkali and hydrogen evolution reaction(HER)in acid.A flow alkali/acid hybrid electrolytic cell(fA/A-hEC)was then developed by coupling anodic GOR with cathodic HER with the Mn-CoSe_(2)/CFC bifunctional electrode.Such fA/A-hEC enables a rather low voltage of 0.54 V to achieve 10 mA cm^(-2),and maintain long-term electrolysis stability over 300-h operation at 100 mA cm^(-2)with Faraday efficiencies of over 99%for H_(2)and 90%for formate production.The designed bifunctional electrode in such innovative fA/A-hEC device provides insightful guidance for coupling energy-efficient hydrogen production with biomass upgradation.

Density Functional Theory Study on the Optical Properties of Mn-doped GaN

The absorption and emission spectra of the wurtzite Mn-doped GaN were calculated with cluster models.The predicted lattice parameters become slightly larger than those of undoped cluster.The average bond length of Mn–N is longer than that of Ga–N.Spin density shows that one Mn atom in these clusters has four single electrons with the same direction of the spin polarity.The new energy level with light Mn-doping appears at 1.37 eV above the valance band.The absorption spectra of Mn-doped GaN cover the visible light region.The calculated emission spectra show that the green luminescence of GaN material in experiment did not result from Mn dopant.With the increase of Mn doping,the emission intensity of yellow or blue band increases to different extent and the band-to-band emission band shows red shift from peak at 3.34 to 3.24 eV.

Structure,room-temperature magnetic and optical properties of Mn-doped TiO_2 nano powders prepared by the sol-gel process

TiO2 nano powders with Mn concentration of 0 at%-12 at% were synthesized by the sol-gel process, and were annealed at 500 ℃ and 800 ℃ in air for 2 hrs. X-ray diffraction （XRD） measurements indicate that the Mn-TiO2 nano powders with Mn concentration of 1 at% and 2 at% annealed at 500 and 800 ℃ are of pure anatase and rutile, respectively. The scanning electron microscope （SEM） observations reveal that the crystal grain size increases with the annealing temperature, and the high resolution transmission electron microscopy （HRTEM） investigations further indicate that the samples are well crystallized, confirming that Mn has doped into the TiO2 crystal lattice effectively. The room temperature ferromagnetism, which could be explained within the scope of the bound magnetic polaron （BMP） theory, is detected in the Mn-TiO2 samples with Mn concentration of 2 at%, and the magnetization of the powders annealed at 500 ℃ is stronger than that of the sample treated at 800 ℃. The UV-VIS diffuse reflectance spectra results demonstrate that the absorption of the TiO2 powders could be enlarged by the enhanced trapped electron absorption caused by Mn doping.

Mn-doped LiFePO_(4)@C as a high-performance cathode material for lithium-ion batteries

In this work,LiFe_(1-x)MnxPO_(4)@C(x=0,0.01,0.02,0.03)cathode materials were obtained by a simple co-precipitation method and heat treatment,and the influence of Mn-doped modification on the electrochemical performance of LiFePO_(4)@C cathode materials was investigated.Results show that by doping an appropriate amount of Mn,the cell volume became larger,and the electronic conductivity increased,which improved the Li+diffusion rate and thus its rate capability and cycle performance of Li-ion batteries.Among them,LiFe_(0.98)Mn_(0.02)PO_(4)@C showed superior lithium storage capability;the discharge capacity can reach 150.7 mAh g^(−1)at 0.1 C.The cell could discharge up to 155.9 mAh g^(−1)at 1 C under high temperature at 45°C,which was higher than LiFePO_(4)@C(142 mAh g^(−1))under the same test conditions.The discharge capacity of 1 C at room temperature was 139.9 mAh g^(−1),and the cycle stability was 95.9%after 200 cycles.It showed that it had good rate capability and excellent cycle performance.These results indicate that Mn-doped LFP is a simple and effective strategy for developing high-performance cathode materials.

Drug delivery with Mn-doped MoO_(2) for photothermalenhanced chemotherapy in fighting cancers

Although chemotherapy has been intensively applied in cancer treatments,its inadequate therapeutic efficacy and severe side effects are still under constant concerns.Nanoplatforms used as anti-tumor drug delivery system(DDS)have attracted tremendous attentions owing to their various intriguing properties.Herein,Mn-doped MoO_(2)nanoparticles coated with ZrO_(2)and capped with Bi_(2)O_(3)have been designed as a DDS,namely MMZB.MMZB possesses good magnetic properties,great photothermal conversion ability,sensitive tumor microenvironment(TME)responsiveness,and good biocompatibility in hemocompatibility in vitro.Thus,MMZB has been utilized to load the chemotherapeutic agent daunomycin(DNM)(MMZB@DNM)for chemo-photothermal combined therapy.MMZB@DNM demonstrates a more impressive anti-cancer effect than the individual photothermal or chemotherapy both in vitro and in vivo.Furthermore,the analysis of tumor specimen sections and serum levels after the treatment indicates negligible side effects for MMZB@DNM in vivo.This contribution provides a valuable concept in designing therapeutic agents for achieving significantly enhanced tumor treatments,which benefits from the synergistic combination of chemotherapy and photothermal therapy in one single nanoagent.

Large-scale synthesis of single-source, thermally stable, and dual-emissive Mn-doped Zn-Cu-ln-S nanocrystals for bright white light-emitting diodes

The global demand for resource sustainability is growing. Thus, the development of single-source, environment-friendly colloidal semiconductor nanocrystal （NC） phosphors with broadband emission spectra is highly desirable for use as color converters in white light-emitting diodes （WLEDs）. We report herein the gram-scale synthesis of single-source, cadmium-free, dual-emissive Mn-doped Zn-Cu-In-S NCs （d-dots） by a simple, non-injection, low-cost, one-pot approach. This synthesis method led to the formation of NCs with continuously varying compositions in a radial direction because each precursor had a different reactivity. Consequently, the d-dots exhibited two emission bands, one that could be attributed to Mn emission and a second that could be ascribed to the band edge of the Zn-Cu-In-S NCs. The emission peaks assigned to band edge were tunable by modifying the particle size and composition. The prepared d-dots also exhibited the characteristic zero self-absorption, a quantum yield of 46%, and good thermal stability. Combining a commercial blue light-emitting diode （LED） chip with optimized d-dots as color converters gave a high color rendering index of up to 90, Commission Internationale de l＇eclairage color coordinates of （0.332, 0.321）, and a correlated color temperature of 5,680 K. These results suggest that cadmium-free, thermally stable, single-phase d-dot phosphors have potential applications in WLEDs.

Photocatalytic oxidation of gaseous benzene,toluene and xylene under UV and visible irradiation over Mn-doped TiO_(2)nanoparticles

The photocatalytic oxidation of gaseous benzene,toluene and xylene(BTX)over un-doped,0.1 and 1 wt%Mn-TiO_(2)nanoparticles under ultraviolet and visible irradiation was studied in atmosphere of synthetic air or inert gas.The photocatalytic decomposition efficiency and the oxidation products were determined using a Static Photochemical Reactor coupled with FTIR spectroscopy.BTX underwent efficient decomposition over Mn-TiO_(2)photocatalysts under UV irradiation,more with oxygen presence and less without oxygen.More important toluene and xylene went substantial decomposition over 0.1 mol%Mn-TiO_(2)under visible irradiation with oxygen presence.The main final oxidation products in the UV photocatalysis of BTX were CO_(2),CO and H2O,with CO_(2) and CO yields 4 and 2 respectively.The conversion percentage of benzene,toluene,and xylene to CO_(2) were 63.6%,56.4%,51.8%,and to CO 29%,26.5%,23.2%,respectively.In the visible photocatalysis of toluene and xylene the yields of CO were insignificant.Formation of carbon containing deposits on TiO_(2)surfaces was observed after extensive UV photocatalysis of toluene and xylene,and such by-products surface coverage may reduce the photocatalytic activity of TiO_(2)samples.Some aspects of the photocatalytic mechanism were examined.

Superoxide dismutase mimetic ability of Mn-doped ZnS QDs

Superoxide dismutase(SOD) is an important antioxidant enzyme in the body. SOD has special physiological activity and is the primary substance for scavenging free radicals in living organisms.However, the expensive and complex extraction processes, low SOD yield, as well as difficult to store at room temperature have seriously hindered its application pace. Herein, the enzyme mimetic function of Mn-doped ZnS quantum dots(QDs) was discovered. The improved Marklund and McCord method both showed that Mn-doped ZnS QDs possess intrinsic SOD-like activity. The effects of temperature and pH on the mimetic enzyme activity of Mn-doped ZnS QDs have been investigated compared with SOD enzymes.The low cost and easy to synthesize white Mn-doped ZnS QDs with good biocompatibility are expected to be used as a new type of SOD nanozymes in the biology-relevant fields.

Synthesis of Multifunctional Mn-Doped CdTe/ZnS Core/Shell Quantum Dots

The synthesis of a novel water-soluble Mn-doped CdTe/ZnS core-shell quantum dots using a proposed ultra- sonic assistant method and 3-mercaptopropionic acid （MPA） as stabilizer is descried. To obtain a high luminescent intensity, post-preparative treatments, including the pH value, reaction temperature, reflux time and atmosphere, have been investigated. For an excellent fluorescence of Mn-doped CdTe/ZnS, the optimal conditions were pH 11, reflux temperature 100℃ and reflux time 3 h under N2 atmosphere. While for phosphorescent Mn-doped CdTe/ZnS QDs, the synthesis at pH 11, reflux temperature 100℃ and reflux time 3 h under air atmosphere gave the best strong phosphorescence. The characterizations of Mn-doped CdTe/ZnS QDs were also identified using AFM, IR, powder XRD and thermogravimetric analysis. The data indicated that the photochemical stability and the photolu- minescence of CdTe QDs are greatly enhanced by the outer inorganic ZnS shell, and the doping Mn2＋ ions in the as-prepared quantum dots contribute to strong luminescence. The strong luminescence of Mn-doped CdTe/ZnS QDs reflected that Mn ions act as recombination centers for the excited electron-hole pairs, attributing to the transition from the triplet state （4T1） to the ground state （6A1） of the Mn2＋ ions. All the experiments demonstrated that the surface states played important roles in the optical properties of Mn-doped CdTe/ZnS core-shell quantum dots.

Mn-doped SiGe thin films grown by UHV/CVD with room-temperature ferromagnetism and high hole mobility

In this work,silicon-germanium(SiGe)thin films are epitaxially grown on Ge substrates by ultra-high vacuum chemical vapor deposition and then doped with Mn element by ion-implantation and subsequent rapid thermal annealing(RTA).The characterizations show that the epitaxial SiGe thin films are single-crystalline with uniform tensile strain and then become polycrystalline after the ion implantation and following RTA.The magnetization measurements indicate that the annealed thin films exhibit Mn concentration-dependent ferromagnetism up to 309 K and the X-ray magnetic circular dichroism characterizations reveal the spin and orbital magnetic moments from the substitutional Mn element.To minimize the influence of anomalous Hall effect,magneto-transport measurements at a high magnetic field up to 31 T at 300 K are performed to obtain the hole mobility,which reaches a record-high value of~1230 cm^(2)V^(-1)s^(-1),owing to the crystalline quality and tensile strain-induced energy band modulation of the samples.The first demonstration of Mn-doped SiGe thin films with roomtemperature ferromagnetism and high carrier mobility may pave the way for practical semiconductor spintronic applications.

Sonochemical synthesis,characterization,and magnetic properties of Mn-doped ZnO nanostructures

Mn-doped ZnO samples,Zn_(1-x)Mn_(x)O(x=0,0.01,0.03 and 0.05;mole fraction),were successfully synthesized by sonochemical method.The undoped and Mn-doped Zn O samples were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),and Raman spectroscopy.XRD patterns of all products are identified to hexagonal wurtzite Zn O structure and their three main peaks shift toward lower diffraction angles due to the incorporation of Mn^(2+)into Zn O crystal lattice.The morphologies of Zn_(1-x)Mn_(x)O(x=0,0.01,0.03 and 0.05)were examined by SEM and TEM.The undoped Zn O sample shows large-scale uniform microflowers which are broken into nanorods and nanoparticles by Mn dopant.Their magnetic properties were investigated by a vibrating sample magnetometer at room temperature.The magnetization-applied field behavior of undoped Zn O defines its weak ferromagnetic behavior.The 3 mol%Mn-doped Zn O shows the highest saturation magnetization of 51.73910^(-3)m A·m^(2)·g^(-1),and the 5 mol%Mn-doped Zn O has suppressed ferromagnetic property due to the formation of Mn clusters inside.

Tunable quantum Shubnikov-de Hass oscillations in antiferromagnetic topological semimetal Mn-doped Cd_(3)As_(2)

Three-dimensional Dirac semimetal Cd_(3)As_(2)has been considered as an excellent candidate for applications of electronic devices owing to its ultrahigh mobility and air-stability.However,current researches are focused mainly on the use of gate-voltage to control its carrier transport tunability,while the manipulation of transport properties by element-doping is quite limited.Here we report the tunable magneto-transport properties by adjusting Mn-doping in the Cd_(3)As_(2)compound.We find that Mnelement doping has a strong influence on the Fermi level positions,and the Fermi energy approaches to Dirac point with higher Mn-doping.More importantly,the introduction of Mn atoms transforms diamagnetic Cd_(3)As_(2)to anti ferromagnetic(Cd,Mn)_(3)As_(2),which provides an approach to control topological protected Dirac materials by ma nipulating antiferro magnetic order parameters.The Shubnikov-de Hass oscillation originates from the surface states,and the Landau fan diagram yields a nontrivial Berry phase,indicating the existence of massless Dirac fermions in the(Cd_(1-x)Mn_x)_(3)AS_(2)compounds.Our present results may pave a way for further investigating anti ferromagnetic topological Dirac semimetal and expand the potential applications in optoelectronics and spintronics.

Hyperfine splitting and ferromagnetism in CdS:Mn nanoparticles for optoelectronic device applications

Manganese(Mn)doped cadmium sulphide(Cd S)nanoparticles were synthesized using a chemical method.It was possible to decrease Cd S:Mn particle size by increasing Mn concentration.Investigation techniques such as ultraviolet-visible(UV-Vis)absorption spectroscopy and photoluminescence(PL)spectroscopy were used to determine optical properties of Cd S:Mn nanoparticles.Size quantization effect was observed in UV-Vis absorption spectra.Quantum efficiency for luminescence or the internal magnetic field strength was increased by doping Cd S nanoparticles with Mn element.Orange emission was observed at wavelength~630 nm due to ^(4)T_1→^(6)A_1 transition.Isolated Mn~(2+)ions arranged in tetrahedral coordination are mainly responsible for luminescence.Luminescence quenching and the effect of Mn doping on hyperfine interactions in the case of Cd S nanoparticles were also discussed.The corresponding weight percentage of Mn element actually incorporated in doping process was determined by atomic absorption spectroscopy(AAS).Crystallinity was checked and the average size of nanoparticles was estimated using the X-ray diffraction(XRD)technique.Cd S:Mn nanoparticles show ferromagnetism at room temperature.Transmission electron microscopy(TEM)images show spherical clusters of various sizes and selected area electron diffraction(SAED)patterns show the polycrystalline nature of the clusters.The electronic states of diluted magnetic semiconductors(DMS)ofⅡ-Ⅵgroup Cd S nanoparticles give them great potential for applications due to quantum confinement.In this study,experimental results and discussions on these aspects have been given.

Microstructure and ferromagnetism of heavily Mn doped SiGe thin flims

Heavily Mn-doped SiGe thin films were grown by radio frequency magnetron sputtering and then treated by postgrowth thermal annealing.Structural characterizations reveal the coexistence of Mn-diluted SiGe crystals and Mn-rich nanoclusters in the annealed films.Magnetic measurements indicate the ferromagnetic ordering of the annealed samples above room temperature.The data suggest that the ferromagnetism is probably mainly contributed by the Ge-rich nanoclusters and partially contributed by the tensile-strained Mn-diluted SiGe crystals.The results may be useful for room temperature spintronic applications based on group IV semiconductors.

Preparation,structure and ferromagnetic properties of the nanocrystalline Ti_(1-x)Mn_xO_2 thin films grown by radio frequency magnetron co-sputtering

This paper reported that the Mn-doped TiO2 films were prepared by radio frequency （RF） magnetron cosputtering. X-ray diffraction measurements indicate that the samples are easy to form the futile structure, and the sizes of the crystal grains grow big and big as the Mn concentration increases. X-ray photoemlssion spectroscopy measurements and high resolution transmission electron microscope photographs confirm that the manganese ions have been effectively doped into the TiO2 crystal when the Mn concentration is lower than 21%. The magnetic property measurements show that the Ti1-xMnxO2 （x = 0.21） films are ferromagnetic at room temperature, and the saturation magnetization, coercivity, and saturation field are 16.0 emu/cm^3, 167.5 × 80 A/m and 3740 × 80 A/m at room temperature, respectively. The room-temperature ferromagnetism of the films can be attributed to the new futile Ti1-xMnxO2 structure formed by the substitution of Mn^4＋ for Ti^4＋ into the TiO2 crystal .lattice, and could be explained by O vacancy （Vo）-enhanced ferromagnetism model.

Room-Temperature Ferromagnetism in Zn1-xMnxO Thin Films Deposited by Pulsed Laser Deposition

Zn1-xMnxO （x = O.Olq3.1） thin films with a Curie temperature above 300K are deposited on Al2O3 （0001） substrates by pulsed laser deposition. X-ray diffraction （XRD）, ultraviolet （UV）-visible transmission and Raman spectroscopy are employed to characterize the microstructural properties of these films. Room temperature ferromagnetism is observed by superconducting quantum interference device （SQUID）. The results indicate that Mn doping introduces the incorporation of Mn^2＋ ions into the ZnO host matrix and the insertion of Mn^2＋ ions increases the lattice defects, which is correlated with the ferromagnetism of the obtained films. The doping concentration is also proven to be a crucial factor for obtaining highly ferromagnetic Zn1-xMnxO films.