High Mn Doping Research Articles

Mn derived growth of CsPbBr3 nanoplatelets for stable and bright orange emission

Abstract Mn-doped perovskites have been extensively studied in optics, magnetism, and electronics due to their orange emission. However, successful Mn doping required a high Mn/Pb feed ratio. In this paper, Mn-doped CsPbBr3 nanoplatelets (NPLs) with bright orange emission were prepared by a two-step slow thermal injection synthesis. The slow injection of precursors effectively slow-down the crystal growth kinetic process and controls the growth of undoped CsPbBr3 NPLs. This process also significantly improves Mn doping efficiency. Mn doping induced the generation of numerous precursor clusters during the growth of CsPbBr3 NPLs, and the formation of these clusters was crucial for enhancing the doping efficiency. The maximum amount of Mn precursor in CsPb0.83Mn0.17Br3 was 50% of Pb precursors. The photoluminescence quantum yields (PLQYs) of CsPb0.94Mn0.06Br3 NPLs reached up to 80.6%, which was 3.1 times of that of CsPbBr3 NPLs. The PL properties of Mn-doped CsPbBr3 NPLs were significantly enhanced compared with pure CsPbBr3 NPLs. The growth process and luminescence mechanism of Mn-doped CsPbBr3 NPLs were discussed. High PLQYs and efficient Mn doping supplied an ideal approach for the preparation of various CsPbX3 (X = Cl, Br, and I) NCs for commercial applications.

Proliferation in the photo-response characteristics of MDC thin films for optoelectronic applications through NSP technique

Nebulizer spray pyrolysis (NSP), a simple thin-film deposition method, was used to fabricate p-Si/n-manganese-doped cerium oxide (MDC)/Al photodiodes. The structure, morphology, optics, composition, electrical and rectifying properties of the prepared materials were analyzed. UV-Vis analysis demonstrates a prominent and acute absorption edge at 425 nm in the visible region. As more Mn impurities are incorporated into CeO2 crystallites, the band gap decreases as the doping level increases, leading to the formation of new recombination sites with low energy emissions. Electrons in outer orbits operate in energy bands, moving to higher energy levels. At higher Mn doping, some NBE emissions and green emission peaks disappear. The emission spectrum confirmed that strong and broad blue emission peak occurred for the diode containing the 15% Manganese Diode Cerium film. XRD peak shows the mono-phase polycrystalline cubic fluorite structure with the main orientation in the 200 directions. The broad lines (CeO) symmetry at 695,659,538 and 517 cm−1 observed in the Fourier Transform -Infrared spectrum are due to the phonons of the cerium oxide (Ce-O) network caused by asymmetric tip stretching and fastening vibration. Satellite peaks arise due to the transition from ligand (O 2p) to metal (Ce 4f) achieved during the primary and main photo-ionization process. This suggests that the valence states of Ce3+ and Ce4+ provide access to the CeO2 lattice sites. The I-V properties of p-Si/n-MDC/Al devices show behavior limited by the properties of the inorganic semiconductor substrate and the size of the hetero-interface energy barrier. The switching voltage of the hetero-junction was found to be approximately 2.4 V.

A comparative study of magnetic (Mn) and non-magnetic (In) elements-doped Bi2Se3 topological insulator: Structural, magnetic, transport, and weak anti-localization property exploration

The present comparative study explores the effect of magnetic (Mn) and non-magnetic (In) doping on structural, magnetic, and quantum-transport properties of Bi2Se3 topological insulator. Un-doped as well as Mn, In-doped Bi2Se3 samples have been synthesized using the solid-state reaction method, confirmed by HR-TEM results. The XRD pattern along with Rietveld refinement reveals that, both Mn and In-dopants substitute the Bi-ion together with slightly interstitially incorporation in host Bi2Se3. It is also found that In-doping is more preferable for Bi-substitution than Mn, which is well supported through our XPS analysis. The study of magnetism indicates the diamagnetic nature of un-doped Bi2Se3 gradually transformed into ferromagnetism for high Mn-doping, whereas In-doped Bi2Se3 shows a mixing of diamagnetism and paramagnetism. Electrical-transport establishes that In-doped Bi2Se3 preserves the hostʼs metallic nature; however, the arrest of metallic response is observed through the evidence of Kondo effect below 185 K for high Mn-doping. Interestingly, the Mn-doping creates a transformation of hostʼs weak anti-localization (WAL) towards weak localization (WL), and produces a significant reduction in the phase coherence length (lφ) of host Bi2Se3, verified by the magneto-conductance analysis. Whereas, In-doping shows relatively minor deviation in hostʼs WAL effect for higher doping limit.

Pr-Doped SrTi0.5Mn0.5O3-δ as an Electrode Material for a Quasi-Symmetrical Solid Oxide Fuel Cell Using Methane and Propane Fuel.

The use of identical electrodes for both the cathode and the anode in a symmetrical solid oxide fuel cell (SSOFC) can simplify the preparation process and increase the durability of the cell, but it is also demanding on the properties of the electrode including stability, electric conductivity, and electrocatalysis. The doping of variable-valence Mn4+/3+2+ on the B site of stable SrTiO3 is explored in this study as both the cathode and the anode for an SSOFC. Though the limit of Mn doping in SrTiO3 is generally low, the additional Pr3+/4+ donor on the Sr site of SrTi0.5Mn0.5O3 was found to enhance the structure stability, electric conductivity, and electrocatalysis. The cell with Pr0.5Sr0.5Ti0.5Mn0.5O3 electrodes excels under H2, propane, or CH4/H2 fuel, providing the cocatalyst was infiltrated on the anode side. The polarization resistance value of Pr0.5Sr0.5Ti0.5Mn0.5O3 was 0.27 Ω·cm2 as the cathode and 0.33 Ω·cm2 for the SSOFC using H2 fuel. The performance under CH4/H2 fuel can be boosted to above 0.9 W cm-2 if Ni/ceria was loaded onto the anode to enhance the methane reforming. This work contributes to a perovskite anode with high Mn doping in SrTiO3 for application in SSOFC for natural gas with renewable H2 injection.

Tunable quantum Shubnikov-de Hass oscillations in antiferromagnetic topological semimetal Mn-doped Cd3As2

Three-dimensional Dirac semimetal Cd3As2 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 Cd3As2 compound. We find that Mn-element 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 Cd3As2 to antiferromagnetic (Cd, Mn)3As2, which provides an approach to control topological protected Dirac materials by manipulating antiferromagnetic 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 (Cd1-xMnx)3As2 compounds. Our present results may pave a way for further investigating antiferromagnetic topological Dirac semimetal and expand the potential applications in optoelectronics and spintronics.

Origin and tunability of dual color emission in highly stable Mn doped CsPbCl3 nanocrystals grown by a solid-state process

Herein, we report on a facile, bulk scale room temperature solid-state synthesis of highly stable and luminescent Mn-doped CsPbCl3 nanocrystal (NCs) with high Mn substitution, and investigate the origin and tunability of its dual-color emission. The structural and compositional analyses confirm the successful doping of Mn (1–40%) ion in CsPbCl3 NCs. The Mn-doped CsPbCl3 NCs exhibit distinct excitonic photoluminescence (PL) emission at ~412 nm (Iex) and Mn related emission at ~590 nm (IMn) with high PL quantum yield (up to 35%). Our study reveals that the intensity ratio IMn/Iex could be widely tuned by a factor of 64 and 23 by changing the Mn concentration and the measurement temperature, respectively. The stronger Mn emission at higher temperature is attributed to the higher rate of transfer of photoexcited carriers from the excitonic state of CsPbCl3 host to Mn related state. Further, excitation intensity-dependent PL along with time-resolved PL studies revealed important insights into the origin and tunability of Mn related orange-red PL in the dual color emitting Mn-doped CsPbCl3 NCs. The PL line shape analysis revealed additional PL peak in the range ~634–666 nm, which grows stronger with higher doping concentration and it is attributed, for the first time, to structural defects in the NCs. Remarkably, the Mn-doped CsPbCl3 NCs synthesized by our method exhibit about 10 times higher storage stability than those reported earlier due to the high Mn doping efficiencies achieved due to the strain induced enhanced doping process. Finally, white light emitting diodes (LEDs) were fabricated by employing blue-emitting CsPbCl1.5Br1.5 NCs, green-emitting CsPbBr3 NCs and orange-red emitting 10% Mn-doped CsPbCl3 NCs all grown by the same method. Our work demonstrates a low-cost synthesis strategy for high Mn doping in CsPbCl3 NCs with superior ambient stability and highly tunable emission.

Enhanced Ferromagnetism in Nanoscale GaN:Mn Wires Grown on GaN Ridges.

The problem of weak magnetism has hindered the application of magnetic semiconductors since their invention, and on the other hand, the magnetic mechanism of GaN-based magnetic semiconductors has been the focus of long-standing debate. In this work, nanoscale GaN:Mn wires were grown on the top of GaN ridges by metalorganic chemical vapor deposition (MOCVD), and the superconducting quantum interference device (SQUID) magnetometer shows that its ferromagnetism is greatly enhanced. Secondary ion mass spectrometry (SIMS) and energy dispersive spectroscopy (EDS) reveal an obvious increase of Mn composition in the nanowire part, and transmission electron microscopy (TEM) and EDS mapping results further indicate the correlation between the abundant stacking faults (SFs) and high Mn doping. When further combined with the micro-Raman results, the magnetism in GaN:Mn might be related not only to Mn concentration, but also to some kinds of built-in defects introduced together with the Mn doping or the SFs.

(Invited) Red-Emitting Manganese-Doped Aluminum Nitride Phosphor

We report high efficiency luminescence with a manganese-doped aluminum nitride red-emitting phosphor under 254 nm excitation, as well as its excellent lumen maintenance in fluorescent lamp conditions, making it a candidate replacement for the widely deployed europium-doped yttria red phosphor. Solid-state reaction of aluminum nitride powders with manganese metal at 1900 °C, 10 atm N2 in a reducing environment results in nitrogen deficiency, as revealed by diffuse reflectance spectra. When these powders are subsequently annealed in flowing nitrogen at 1650 °C, higher nitrogen content is recovered, resulting in white powders. Silicon was added to samples as an oxygen getter to improve emission efficiency. NEXAFS spectra and DFT calculations indicate that the Mn dopant is divalent. From DFT calculations, the UV absorption band is proposed to be due to an aluminum vacancy coupled with oxygen impurity dopants, and Mn2+ is assumed to be closely associated with this site. In contrast with some previous reports, we find that the highest quantum efficiency with 254 nm excitation (Q.E. = 0.86±0.14) is obtained in aluminum nitride with a low manganese doping level of 0.06 mol%. The principal Mn2+ decay of 1.25 ms is assigned to non-interacting Mn sites, while additional components in the microsecond range appear with higher Mn doping, consistent with Mn clustering and resultant exchange coupling. Slower components are present in samples with low Mn doping, as well as strong afterglow, assigned to trapping on shallow traps followed by detrapping and subsequent trapping on Mn. Figure 1

High-spin configuration of Mn in Bi2Se3 three-dimensional topological insulator

Electron paramagnetic resonance was used to investigate Mn impurity in Bi2Se3 topological insulator grown by the vertical Bridgman method. Mn in high-spin S=5/2, Mn2+, configuration was detected regardless of the conductivity type of the host material. This means that Mn2+(d5) energy level is located within the valence band, and Mn1+(d6) energy level is outside the energy gap of Bi2Se3. The electron paramagnetic resonance spectrum of Mn2+ in Bi2Se3 is characterized by the isotropic g-factor |g|=1.91 and large axial parameter D=−4.20GHzh. This corresponds to the zero-field splitting of the Kramers doublets equal to 8.4GHzh and 16.8GHzh, respectively, which is comparable to the Zeeman splitting for the X-band. Mn in Bi2Se3 acts as an acceptor, effectively reducing native-high electron concentration, compensating selenium vacancies, and resulting in p-type conductivity. However, Mn-doping simultaneously favors formation of native donor defects, most probably selenium vacancies. For high Mn-doping it may lead to the resultant n-type conductivity related with strong non-stoichiometry and degradation of the crystal structure - switching from Bi2Se3 to BiSe phase.

Red-emitting manganese-doped aluminum nitride phosphor

We report high efficiency luminescence with a manganese-doped aluminum nitride red-emitting phosphor under 254nm excitation, as well as its excellent lumen maintenance in fluorescent lamp conditions, making it a candidate replacement for the widely deployed europium-doped yttria red phosphor. Solid-state reaction of aluminum nitride powders with manganese metal at 1900°C, 10atmN2 in a reducing environment results in nitrogen deficiency, as revealed diffuse reflectance spectra. When these powders are subsequently annealed in flowing nitrogen at 1650°C, higher nitrogen content is recovered, resulting in white powders. Silicon was added to samples as an oxygen getter to improve emission efficiency. NEXAFS spectra and DFT calculations indicate that the Mn dopant is divalent. From DFT calculations, the UV absorption band is proposed to be due to an aluminum vacancy coupled with oxygen impurity dopants, and Mn2+ is assumed to be closely associated with this site. In contrast with some previous reports, we find that the highest quantum efficiency with 254nm excitation (Q.E.=0.86±0.14) is obtained in aluminum nitride with a low manganese doping level of 0.06mol.%. The principal Mn2+ decay of 1.25ms is assigned to non-interacting Mn sites, while additional components in the microsecond range appear with higher Mn doping, consistent with Mn clustering and resultant exchange coupling. Slower components are present in samples with low Mn doping, as well as strong afterglow, assigned to trapping on shallow traps followed by detrapping and subsequent trapping on Mn.

Identifying the Electronic Character and Role of the Mn States in the Valence Band of (Ga,Mn)As

We report high-resolution hard x-ray photoemission spectroscopy results on (Ga,Mn)As films as a function of Mn doping. Supported by theoretical calculations we identify, for both low (1%) and high (13%) Mn doping values, the electronic character of the states near the top of the valence band. Magnetization and temperature-dependent core-level photoemission spectra reveal how the delocalized character of the Mn states enables the bulk ferromagnetic properties of (Ga,Mn)As.

Structural and Optical Properties of Nanostructured Zn<sub>1-X</sub>Mn<sub>x</sub>O Thin Films

Mn doped ZnO films with different doping concentration were synthesized by sol gel method using the spin coating technique. Zn1-xMnxO thin films are prepared using 2-methoxyethanol solution of zinc acetate dehydrate and manganese acetate tetrahydrate. The quantity of Mn in the sol was synthesized with undoped ZnO, 2%, 4%, 6% and 8 % of Mn doped ZnO with an annealing temperature of 500°C. The FESEM images showed many spherical shaped nanoparticles on the cross-sectional of the films. The optical properties were characterized using UV-Vis where the transmittance and band gap value were affected by certain amount of Mn concentration. These films achieve tunable band gap characteristics by means of changing the dopant concentration. It shows an initial decrease of band gap for small concentrations of Mn, followed by an increase at higher Mn doping concentrations.

Structure and magnetic properties of Sn1−xMnxO2

The microstructure and magnetic properties have been investigated systematically for Sn1−xMnxO2 polycrystalline powder samples with x=0.02–0.08 synthesized by a solid-state reaction method. X-ray diffraction revealed that all samples are pure rutile-type tetragonal phase and the cell parameters a and c decrease monotonously with the increase in Mn content, which indicated that Mn ions substitute into the lattice of SnO2. Magnetic measurements revealed that all samples exhibit room temperature ferromagnetism. Furthermore, magnetic investigations demonstrate that magnetic properties strongly depend on doping content, x. The average magnetic moment per Mn atom decreases with increase in the Mn content, because antiferromagnetic super-exchange interaction takes place within the neighbor Mn3+ ions through O2− ions for the samples with higher Mn doping. Our results indicate that the ferromagnetic property is intrinsic to the SnO2 system and is not a result of any secondary magnetic phase or cluster formation.

Effects of Mn substitution on ferro- and piezoelectric properties of Bi0.86Sm0.14FeO3 thin films

The Bi0.86Sm0.14FeO3 (BSFO) and Bi0.86Sm0.14Fe1−xMnxO3 (BSFMO) (x=0.01, 0.03, 0.05) thin films were deposited on indium tin oxide/glass substrates via a metal organic deposition method. 1at.% Mn doping leads to an evident reduction of the leakage current in BSFO film. More importantly, the Bi0.86Sm0.14Fe0.99Mn0.01O3 film exhibits the lowest coercive field (Ec=272kV/cm), the largest remanent polarization (Pr=53.6μc/cm2) and the remanent out-of-plane piezoelectric coefficient (d33=146pm/V). However, further increase of Mn doping content results in the deterioration of the charge retaining capability and the piezoelectric properties of the films. The negative influence of high Mn doping contents was discussed based on the structure change and the contribution of irreversible movement of non-180° domain walls in the aged films.

Enhanced Piezoelectric Properties in Mn-Doped 0.98K0.5Na0.5NbO3-0.02BiScO3Lead-Free Ceramics

Mn-doped 0.98K0.5Na0.5NbO3–0.02BiScO3 (0.98KNN–0.02BS) lead-free piezoelectric ceramics have been prepared by a conventional sintering technique and the effects of Mn doping on the phase structure and piezoelectric properties of the ceramics have been studied. Our results reveal that a small amount of Mn can improve the densification of the ceramics effectively. Because of the high densification, fine grain, and Mn doping effects, the piezoelectric and dielectric properties of the ceramics are improved considerably. Very good piezoelectric and dielectric properties of d33=288 pC/N, kp=0.46, ɛr=1591, and TC=328°C were obtained for the 0.98KNN–0.02BS ceramics doped with 0.8 mol% Mn. Therefore, the 0.98KNN–0.02BS ceramics containing a small amount of Mn are a good candidate material for lead-free piezoelectric ceramics.

Properties of FINEMET with Fe partially replaced by Mn

Thin films and foils of Fe73.5−xSi13.5B9Cu1Nb3Mnx, the FINEMET based amorphous and nanocrytalline alloys with high Mn doping (x=9, 11, 13, 15at%), were studied by means of transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and with Mössbauer spectroscopy (MS), as-quenched (a-q) and after annealing (a). Mn, partially replacing Fe, causes common crystallisation temperature Tcr for the identified crystal structures, decrease of the lattice constants a0, c0, decrease of hyperfine parameters: magnetic field Hhf and isomer shift IS for amorphous phases and in consequence the Curie temperature TCu.

Structural study of MnxSi1-x magnetic semiconductor thin films

The structure of MnxSi1-x magnetic semiconductor thin films prepared by molecular beam epitaxy(MBE) on Si(100) substrate at 600 ℃ has been studied by X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) technique. The XRD results show that in the MnxSi1-x thin films with high Mn doping concentrations (x=0.08 and 0.17), only diffraction peaks of crystalline Mn4Si7 are observed. XANES results indicate that all the Mn K-edge XANES spectra of MnxSi1-x thin films with different Mn doping concentrations (x=0.007, 0.03, 0.08 and 0.17) show the similar feature. XANES calculation based on multiple-scattering theory further reveals that the experimental spectra for samples with different Mn doping concentrations are reproduced by the calculated Mn4Si7 spectrum. These results reveal that for the MnxSi1-x magnetic semiconductor thin films, Mn atoms mainly exist in the Si thin film substrate in the form of Mn4Si7 nanocrystalline grains, the substitutional or interstitial Mn atoms scarcely exist.

Mn, Cu Doping and Optical Properties of Highly Crystalline Ultralong ZnS Nanowires

Manganese (Mn) and copper (Cu) doping of ZnS nanowires was achieved by thermal evaporation of Mn, Cu doped ZnS nanopowders. Field emission scanning electron microscopy, and X-ray diffraction studies of the obtained ZnS nanowires demonstrate that the nanowires are single crystal structures and have diameters about 30-200 nm and lengths up to 1 millimeter. Room temperature photoluminescence (PL) measurements show a common PL peak around 520 nm for all ZnS nanowires samples, while impurity-related emission band are observed in doped ZnS nanowires. The dependence of the PL intensity on Mn doping concentration has also been investigated. It is shown that for high Mn doping concentration (10%) in the starting ZnS nanopowders, new emission bands (orange-red and red bands) are observed from the ZnS:Mn nanowires products. The origins of these new emission bands are discussed and brought up for further discussion.

Structure of MnxGe1－x dilute magnetic semiconductor films

The structure of MnxGe1-x dilute magnetic semiconductor thin films prepared by magnetron co-sputtering has been studied by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) techniques. The XRD results show that in the MnxGe1-x thin film with low Mn doping concentration (x=0.070), only diffraction peaks attributed to crystalline Ge can be observed. In samples with high Mn doping concentrations (x=0.250, 0.360), the secondary phase Ge3Mn5 appears, and its content enhances with Mn doping concentration. The XAFS results indicate that for the Mn0.07Ge0.93 thin film, Mn atoms are mainly incorporated into the Ge lattice and located at the substitutional sites of Ge atoms with the ratio of 75%, while for the Mn0.25Ge0.75 and Mn0.36Ge0.64 samples, most of the Mn atoms are aggregated to form Ge3Mn5.

Magnetic and electrical transport properties of delta-doped amorphous Ge:Mn magnetic semiconductors

We report on the growth and characterization of delta-doped amorphous Ge:Mn diluted magnetic semiconductor thin films on GaAs (0 0 1) substrates. The fabricated samples exhibit different magnetic behaviors, depending on the Mn doping concentration. The Curie temperature was found to be dependent on both the Mn doping concentration and spacing between the doping layers. A sharp drop in magnetization and rise in resistivity are observed at low temperature in samples with high Mn doping concentrations, which is also accompanied by a negative thermal remanent magnetization (TRM) in the higher temperature range. The temperature at which the magnetization starts to drop and the negative TRM appears show a correlation with the Mn doping concentration. The experimental results are discussed based on the formation of ferromagnetic regions at high temperature and antiferromagnetic coupling between these regions at low temperature.