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1.
The mechanism of the enhancement in the ionic conductivity resulting from cubic phase stabilization in MgO partially stabilized zirconia (MgPSZ) by Mn doping was studied by examining the local Zr‐O structure. Cubic phase (14 vol%) in MgPSZ was increased with the addition of MnO2, and 10 mol% Mn‐doped MgPSZ exhibited the highest cubic phase fraction (98.72%), which was analyzed by Rietveld refinement. In addition, only the cubic phase, not the monoclinic and tetragonal phases, was observed in the TEM‐SAED pattern of 10 mol% Mn‐doped MgPSZ. Doped Mn exhibited a high Mn2+/Mn4+ ratio, which was identified by X‐ray photoelectron spectroscopy (XPS). In addition, it indicates that oxygen vacancy formation by substitution of Mn2+ in the Zr4+ site in MgPSZ increased cubic phase fraction. Ionic conductivity of MgPSZ was improved by the cubic phase increase attributed to Mn doping, and 10 mol% Mn‐doped MgPSZ exhibited higher ionic conductivity than MgPSZ. To investigate the mechanism of the ionic conductivity improvement, Zr‐O local structure in Mn‐doped MgPSZ was analyzed by Zr K‐edge EXAFS of MgPSZ, and the number of bonding of the Zr‐O first shell decreased with increased Mn substitution. Therefore, it was considered that the oxygen vacancy generation led to an increase in the cubic phase and the number of ionic conduction sites.  相似文献   

2.
Multiferroic Bi1?xLaxFeO3 [BLFO (x)] ceramics with x = 0.10–0.50 and Mn‐doped BLFO (x = 0.30) ceramics with different doping contents (0.1–1.0 mol%) were prepared by solid‐state reaction method. They were crystallized in a perovskite phase with rhombohedral symmetry. In the BLFO (x) system, a composition (x)‐driven structural transformation (R3cC222) was observed at x = 0.30. The formation of Bi2Fe4O9 impure phase was effectively suppressed with increasing the x value, and the rhombohedral distortion in the BLFO ceramics was decreased, leading to some Raman active modes disappeared. A significant red frequency shift (~13 cm?1) of the Raman mode of 232 cm?1 in the BLFO ceramics was observed, which strongly perceived a significant destabilization in the octahedral oxygen chains, and in turn affected the local FeO6 octahedral environment. In the Mn‐doped BLFO (x = 0.30) ceramics, the intensity of the Raman mode near 628 cm?1 was increased with increasing the Mn‐doping content, which was resulted from an enhanced local Jahn–Teller distortions of the (Mn,Fe)O6 octahedra. Electron microscopy images revealed some changes in the ceramic grain sizes and their morphologies in the Mn‐doped samples at different contents. Wedge‐shaped 71° ferroelectric domains with domain walls lying on the {110} planes were observed in the BLFO (x = 0.30) ceramics, whereas in the 1.0 mol% Mn‐doped BLFO (x = 0.30) samples, 71° ferroelectric domains exhibited a parallel band‐shaped morphology with average domain width of 95 nm. Dielectric studies revealed that high dielectric loss of the BLFO (x = 0.30) ceramics was drastically reduced from 0.8 to 0.01 (measured @ 104 Hz) via 1.0 mol% Mn‐doping. The underlying mechanisms can be understood by a charge disproportion between the Mn4+ and Fe2+ in the Mn‐doped samples, where a reaction of Mn4+ + Fe2+→Mn3+ + Fe3+ is taken place, resulting in the reduction in the oxygen vacancies and a suppression of the electron hopping from Fe3+ to Fe2+ ions effectively.  相似文献   

3.
Electromechanical properties and high power characteristics of Pb‐free hard piezoelectric ceramics in the (BiNa0.88K0.08Li0.04)0.5 (Ti1?xMnx)O3 (= 0, 0.014, 0.015, and 0.016) system were studied. Mn doping resulted in a considerable enhancement of mechanical quality factor Qm and vibration velocity. The lowest mechanical and dielectric losses were achieved in 1.5 mol% Mn‐doped ceramics with a planar Qm of about 970 and tanδ of 0.89%. The heat dissipation and resonance frequency shift under high drive condition were remarkably suppressed upon Mn doping. The maximum vibration velocity was increased from 0.28 m/s in undoped ceramic to 0.6 m/s in 1.5 mol% Mn‐doped composition. The results of this study revealed that Mn‐doped BNT‐based piezoelectrics exhibited a superior high power performance compared to their lead‐based counterparts such as PZT4 and PZT8 ceramics.  相似文献   

4.

Abstract  

A series of Zn2+ and W6+ doped tin oxide (SnO2) thin films with various dopant concentrations were prepared by spray pyrolysis deposition, and were characterized by X-ray diffraction, atomic force microscopy, contact angle, absorbance, current density–voltage (J–V) and photocurrent measurements. The results showed that W6+ doping can prevent the growth of nanosized SnO2 crystallites. When Zn2+ ions were used, the crystallite sizes were proved to be similar with the undoped sample due to the similar ionic radius between Zn2+ and Sn4+. Regardless of the dopant ions’ type or concentration, the surface energy has a predominant dispersive component. By using Zn2+ dopant ions it is possible to decrease the band gap value (3.35 eV) and to increase the electrical conductivity. Photocatalytic experiments with methylene blue demonstrated that with zinc doped SnO2 films photodegradation efficiencies close to 30% can be reached.  相似文献   

5.
Bismuth‐, lanthanum‐, and molybdenum‐doped calcium manganite (CaMnO3, abbreviated Mn113) are synthesized by solid‐state synthesis route from their respective oxide precursors at a same doping level (x=0.05). Depending on the ionic sizes, trivalent dopants (Bi3+ and La3+) replace Ca2+(A site), while penta/hexavalent dopant Mo5+/Mo6+ replaces Mn4+ (B site) in the Mn113 structure. XRD of all three doped samples confirm formation of single phase. In all three samples, doping causes unit cell volume to expand, while volume expansion is maximum for the Mo‐Mn113. The transport behavior of the doped samples follows small polaron hopping mechanism. Resistivity of the doped samples depends not only on the carrier concentration but also on the effective bandwidth determined by the structural distortion introduced by the dopant ions. Bi‐Mn113 has highest resistivity at the both temperature end, while La‐Mn113 has the lowest. Thermopower is determined by the carrier concentration only and does not depend on dopant type, having value ~260 μV/K at 1000 K. At high (>800 K), S reaches a saturation value and becomes independent of T. La‐Mn113 is having highest figure of merit (zT) 0.19 at 1000 K.  相似文献   

6.
The phases present and their crystal structure and microstructure in the nanocrystalline SnO2–TiO2 system were studied in the compositional range Sn1?xTixO2 (0.0 ≤ x ≤ 0.9). There is an apparent increase in the solubility limits in the solid solution compared to bulk crystalline SnO2–TiO2. No two phase region was observed with increasing TiO2 content. Electron energy loss spectroscopy, infrared spectroscopy (FTIR), and X‐ray diffraction (XRD) of the nanopowders showed that the apparent increase in solubility is related to the systematic Ti4+ segregation on the particle surface (surface excess) at the SnO2‐rich side, avoiding the nucleation of a second phase even at high Ti4+ contents. Is this finding in accord with Raman spectra, which suggest localized Ti‐rich sites in the absence of a second crystalline phase. Ti4+ surface excess is also lead to a modification of the surface hydroxyls and a decrease in the crystallite size of the nanoparticles (with a concomitant increase in surface area), with expected implications to catalytic and sensorial properties of these nanoparticles.  相似文献   

7.
Effect of Mn dopant on energy storage properties in lead‐free NaNbO3?0.04CaZrO3 (NNCZ) thin films was investigated. The leakage current was largely suppressed, whereas dielectric constant, breakdown fields, and the difference between maximum polarization and remnant polarization were improved significantly by Mn doping, resulting in a large enhancement of energy storage performance. A large recoverable energy storage density of ~19.64 J/cm3 and an excellent thermal stability (from 30 to 160°C) were simultaneously achieved in the NNCZ thin film with 1 mol% Mn addition. Our results ascertain the great potential of NNCZ lead‐free thin films for the applications in energy storage devices over a wide temperature range.  相似文献   

8.
The Mn4+ activated fluostannate Na2SnF6 red phosphor was synthesized from starting materials metallic tin shots, NaF, and K2MnF6 in HF solution at room temperature by a two‐step method. The formation mechanism responsible for preparing Na2SnF6:Mn4+ (NSF:Mn) has been investigated. The influences of synthetic parameters: such as concentrations of HF and K2MnF6 in reaction system, reaction time, and temperature on crystallinity, microstructure, and luminescence intensity of NSF:Mn have been investigated based on detailed experimental results. The actual doping concentration of Mn4+ in the NSF:Mn host lattice is less than 0.12 mol%. The most of K2MnF6 is decomposed in HF solution especially in hydrothermal system at elevated temperatures. The color of the as‐prepared NSF:Mn samples changes from orange to white when the temperature is higher than 120°C, which indicates the lower concentration of luminescence centers in the crystals. A series of “warm” white light‐emitting diodes with color rendering index (CRI) higher than 88 and correlated color temperatures between 3146 and 5172 K were obtained by encapsulating the as‐prepared red phosphors NSF:Mn with yellow one Y3Al5O12:Ce3+ (YAG:Ce) on 450 nm blue InGaN chips. The advantage of the synthetic strategy to obtain NSF:Mn can be extended to developing Mn4+‐doped red phosphors from low‐costing metals at room temperature for large‐scale industrial applications.  相似文献   

9.
To fulfil the demands of high-power plant growth lamps, cation co-doping is an effective way to tune the photoluminescence properties of manganese (Ⅳ)-activated aluminate phosphors. Therefore, we managed to synthesize a series of cations co-doped CaYAlO4:xMn4+, mSr2+, M+ (M+ = Li+, Na+, and K+) (CYAO:Mn, Sr, M) far-red-emitting phosphors. The excitation spectrum of these phosphors contained two excitation bands, and the opposite effects of these two bands on the luminescence intensity have been observed with the increase of Mn4+ concentration. By adding 0.1 mol Sr2+ ions to replace Ca2+ site, the emission intensity and thermal stability of CYAO:Mn phosphors can be enhanced. Furthermore, the luminescence properties of CSYAO:Mn can be further improved by co-doping monovalent alkali metal ions to serve as charge compensators, the increased number of Mn4+ luminescence centers. Moreover, 0.6 mol% Na+ can increase the initial emission intensity of the phosphors by 117% as the best ratio. The characteristic emission spectrum of the phosphors CYAO:Mn,Sr,M correspond to the phytochrome PFR of plants. These experiments and characterization results have certified that these phosphors have a potential application in indoor plants cultivation.  相似文献   

10.
Highly transparent, p-type conducting SnO2:Zn films were deposited on quartz substrates by radio frequency (RF) magnetron sputtering using a 12 wt% ZnO doped with 88 wt% SnO2 ceramic target followed by annealing at various temperatures. The effect of annealing temperature on the structural, electrical and optical performances of SnO2:Zn films has been studied. XRD results show that all the SnO2:Zn films possess tetragonal rutile structure with the preferred orientation of (101). Hall effect results indicate that at 873 K for 3 h was the optimum annealing parameters for p-type SnO2:Zn films with relatively high hole concentration and low resistivity of 3.334 × 1019 cm−3 and 3.588 Ω cm, respectively. The average transmission of the p-type SnO2:Zn films were above 80% in the visible light range. In addition, p-type conductivity was also confirmed by the non-linear characteristics of a p-type SnO2:Zn/n-type SnO2:Sb structure.  相似文献   

11.
The effect of high doping levels of manganese (Mn) on the structure and electrical properties of (KxNa1?x)NbO3 (KNN) ceramics containing Li, Ta, and Sb has been investigated. The samples were measured using synchrotron X‐ray diffraction whereas Rietveld refinement with Fullprof was used to determine the structural information as a function of temperature. Temperature‐dependent dielectric measurement was used to compare the phase transition temperatures. The results show that Mn decreases the temperature range of phase coexistence between the orthorhombic and tetragonal phase from ~180°C to ~120°C. The Curie temperature remained unchanged with Mn addition while the dielectric constant and dielectric loss increased with Mn addition. High amounts of Mn led to a reduction in both piezoelectric and ferroelectric properties. The remnant polarization, remnant strain, and piezoelectric coefficient values decreased from 24 μC/cm2, 0.000824, 338 ± 37 pm/V to 13 μC/cm2, 0,00014 and 208 ± 27 pm/V, respectively for the undoped and 5 mol% Mn‐doped sample.  相似文献   

12.
《Ceramics International》2023,49(18):30060-30075
In the present work, spray pyrolysis method was adopted to synthesis nano thin films of Sn1-xNdxO2 (x = 0.01 to 0.1) possessing tetragonal structure with (1 1 0) plane orientation. Nd doping reduced the overall crystallinity of the films, however Sn0.92Nd0.08O2 film showed crystallite size of 18.7 nm, similar to that of the pure film. The morphology changed to distinct grains at lower doping concentration, beyond which a fibrous nature evolved but again changed to smaller grains with further increase in the doping. The oxidation states of the constituent elements were confirmed using XPS. The transmittance of the films reduced due to incorporation of Nd ions. A decrease in the energy band gap was also noticed in the films following dopant addition. The PL emissions corresponding to the Nd ion transitions was found in the NIR region resulting from internal 4f-shell transitions of Nd3+ ions. Other defect related emissions like the one from oxygen vacancies also showed up in the UV and visible wavelength regions, which were responsible for a near white light emission. The third-order optical nonlinearity of the films was confirmed using the Z-scan technique. All the Sn1-xNdxO2 films till 8 at. % of doping showed reverse saturable absorption. The highest and lowest nonlinear absorption coefficient was exhibited by Sn0.92Nd0.08O2 and Sn0.98Nd0.02O2 films, respectively. Depending on the Nd concentration, the films either showed self-focusing or self-defocusing behavior and influenced the nonlinear refractive indices of the films. The least optical limiting values among the doped films was obtained in the range of 1.73 kJ/cm2 for Sn0.92Nd0.08O2 films.  相似文献   

13.
In the present work, Zn2SnO4 nanoparticles were doped with silicon to improve their electrical and optical properties by the conventional solid‐state reaction method. The results showed that the minimum electrical resistivity of about 0.09 Ωcm was obtained for Zn2SnO4 nanoparticles with 3% Si doping. The decrease in the electrical resistivity can be attributed to the insertion of Si+4 atoms into the Zn+2 and/or Sn+4 sites and also the formation of more oxygen vacancies in the Zn2SnO4 lattice. The formation of the more oxygen vacancy defect states in Si‐doped Zn2SnO4 nanoparticles was verified by photoluminescence spectroscopy. The efficiency of a dye‐sensitized solar cell based on 3% Si‐doped Zn2SnO4 was significantly better, by about 81%, compared to that of a cell based on the undoped Zn2SnO4. The enhancement in the efficiency can be ascribed to the facilitation of electron transport throughout a photoelectrode due to increase in the charge carrier concentration which was caused by Si doping.  相似文献   

14.
We have successfully synthesized Sn1?xNixO2 (0.05 ≤ x ≤ 0.15) solid solutions in order to study their structural, optical, and magnetic properties at different Ni concentrations. X‐ray diffraction showed monophasic and crystalline tetragonal structure. The shifting of peaks toward higher angle is attributed to the incorporation of Ni2+ ions in SnO2 host lattice. Particle growth restrained upon Ni‐doping and found to be in the range of 8–12 nm. Ni‐doped SnO2 nanoparticles show blue shift in band gap studies, which is found to be in the range of 3.9–4.1 eV. High surface areas have been achieved for these solid solutions, which come out to be 130, 200, 457, 497, and 680 m2/g, respectively. The solid solutions exhibit paramagnetic behavior along with antiferromagnetic exchange coupling.  相似文献   

15.
《Ceramics International》2016,42(15):17128-17136
Nanoparticles of basic composition Sn0.94Zn0.05Co0.01O2, Sn0.92Zn0.05Co0.03O2 and Sn0.90Zn0.05Co0.05O2 were synthesized by chemical precipitation method. The incorporation of Co and Zn in SnO2 lattice introduced significant changes in the physical properties of all the three nanocrystals. The average particle size estimated from TEM data decreased from 15.71 to 6.41  nm with enhancement in concentration of oxygen vacancies as Co content is increased from 1 to 5 wt%. Increasing Co content enhanced the Sn:O atomic ratio as a result concentration of oxygen vacancies increased. The dielectric study revealed strong doping dependence. The dielectric parameters (ε′, tanδ and σac) increased with increasing Co content and attained maximum values for 5% (Zn, Co) co-doped SnO2 nanoparticles. The dielectric loss (ε′′) exhibited dispersion behavior and the Debye’s relaxation peaks observed in dielectric loss factor (tanδ), whose intensities increased with increasing Co content. The variation of dielectric properties and ac conductivity revealed that the dispersion is due to Maxwell-Wagner interfacial polarization and hopping of charge carriers between Sn+2/Sn+3 and Co+2/Co+3. The large dielectric constant of all samples made them interesting materials for device application. Magnetization measurements (M (H) loops) revealed enhancement in saturation magnetization with doping which is due to the formation of large amount of induced defects and oxygen vacancies in the samples. The present study clearly reveals doping dependent properties and the oxygen vacancies induced ferromagnetism in Zn, Co co-doped SnO2 nanoparticles having applications in ultra-high dielectric materials, high frequency devices and spintronics.  相似文献   

16.
Na‐ion conducting Na1+x[SnxGe2?x(PO4)3] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe2(PO4)3 (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe2(PO4)3] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO6) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO4). The highest bulk Na+ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na1.5[Sn0.5Ge1.5(PO4)3]) of tetrahedral Ge4+ ions by Sn4+ on Na–Ge–P network. CV studies of the best conducting Na1.5[Sn0.5Ge1.5(PO4)3] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.  相似文献   

17.
Nb and Mn were doped, respectively, to 0.8Pb(Sn0.46Ti0.54)O3–0.2Pb(Mg1/3Nb2/3)O3 (PST–PMN) to improve electrical properties for meeting the requirement in various fields. The additions of Nb and Mn influence in a pronounced way the structure, and improve the densities of the ceramics. Nb‐doped PST–PMN increased the piezoelectric coefficient d33, planar electromechanical coupling kp, and relative dielectric constant ε, indicating “soft” piezoelectric behavior. Mn doping played a “hard” part, which significantly enhanced the mechanical quality factor Qm without deteriorating other piezoelectric properties. The most excellent properties of Nb‐doped PST–PMN were obtained with doping amount of 0.75 mol%, specifically d33, kp, being on the order of 455 pC/N, 57.5% and 3560, respectively. The addition of 0.75 mol% Mn for PST–PMN presented the optimum electrical properties, with Qm of 554, d33 of 430 pC/N, kp of 57.0%, ε of 2770. It was proposed that the addition of Nb, Mn generated different defect dipoles involved in the domain walls motion and intrinsic piezoelectric responses, leading to different effects on electrical properties.  相似文献   

18.
TiO2 thin films doped with ≤7 mol% Mn (metal basis) were deposited on F-doped SnO2-coated (FTO) glass substrates by spin coating. The structural, morphological, and optical properties of the films were investigated by glancing angle X-ray diffraction (GAXRD), laser Raman microspectroscopy, field emission scanning electron microscopy (FESEM), and ultraviolet–visible spectroscopy (UV–VIS). Mn doping of TiO2 (anatase) extended the optical absorption edge to longer wavelengths (lower photon energies) significantly lowering the band gap from 3.32 eV (undoped) to 2.90 (7 mol% Mn). The absorption edges of all films were sharp and the transparencies in the visible region were in the range 60–75%. All of the films were homogeneous, fully dense, and essentially crack-free.  相似文献   

19.
Nanocrystalline LiFe1−xSnxPO4 (0 ≤ x ≤ 0.07) samples are synthesized using SnCl4·5H2O as dopant via an inorganic-based sol–gel method. The dependency of the physicochemical and electrochemical properties on the doping amount of tin are systemically worked out and regular changes are revealed. In the whole concentration range, the chemical valence of Fe2+ is not basically changed whereas tin is found in two different oxidation states, namely +2 and +4. The replacement of Fe2+ by supervalent Sn4+ would lead to electron compensation. Under the synergetic effects between the charge compensation and the crystal distortion, the electrical conductivities for the bulk samples first increase and then decrease with the increasing amount of Sn doping. Upon the doping amount, the apparent lithium-ion diffusion coefficient and the electrochemical performance also display the similar trends. The doping is beneficial to refine the particle size and narrow down the size distribution, however optimizing the doping amount is necessary. Compared with other samples, the sample with a doping amount of about 3 mol% delivers the highest capacities at all C-rates and exhibits the excellent rate capability due to the high electrical conductivity and the fast lithium-ion diffusion velocity.  相似文献   

20.
BaTiO3 based ceramics (with some additives such as ZrO2, SnO2, etc.) were prepared by solid state reaction. Mn2+ or Mn3+ as an acceptor substituting for Ti4+ in B site and Bi3+ as a donor substituting for Ba2+ in A site were co-doped in BaTiO3 based ceramics. The dielectric properties of BaTiO3 based ceramics co-doped with Bi/Mn were investigated. The results show that the dielectric properties of BaTiO3 based ceramics co-doped with Bi/Mn are affected by the mole ratio of donor and acceptor (Bi/Mn). When the mole ratio of donor and acceptor is high, dielectric dispersion behavior was observed and the dielectric constant decrease and remnant polarization, coercive field and piezoelectric constant will varied. When Bi varied from 1.0% to 2.0 mol% (Mn = 0.8 mol%), remnant polarization from 10.35 to 2.25 μC/cm2, coercive field from 4 to 2.75 kV/cm, and piezoelectric constant d33 from 137 to 36 pC/N respectively.  相似文献   

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