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1.
By modifying the entangled multi-degrees of freedom of transition-metal oxides, interlayer coupling usually produces interfacial phases with unusual functionalities. Herein, a symmetry-mismatch-driven interfacial phase transition from paramagnetic to ferromagnetic state is reported. By constructing superlattices using CaRuO3 and SrTiO3, two oxides with different oxygen octahedron networks, the tilting/rotation of oxygen octahedra near interface is tuned dramatically, causing an angle increase from ≈150° to ≈165° for the Ru O Ru bond. This in turn drives the interfacial layer of CaRuO3, ≈3 unit cells in thickness, from paramagnetic into ferromagnetic state. The ferromagnetic order is robust, showing the highest Curie temperature of ≈120 K and the largest saturation magnetization of ≈0.7 µB per formula unit. Density functional theory calculations show that the reduced tilting/rotation of RuO6 octahedra favors an itinerant ferromagnetic ground state. This work demonstrates an effective phase tuning by coupled octahedral rotations, offering a new approach to explore emergent materials with desired functionalities.  相似文献   

2.
Ferromagnetic materials with a strong spin-orbit coupling (SOC) have attracted much attention in recent years because of their exotic properties and potential applications in energy-efficient spintronics. However, such materials are scarce in nature. Here, a proximity-induced paramagnetic to ferromagnetic transition for the heavy transition metal oxide CaRuO3 in (001)-(LaMnO3/CaRuO3) superlattices is reported. Anomalous Hall effect is observed in the temperature range up to 180 K. Maximal anomalous Hall conductivity and anomalous Hall angle are as large as ∼15 Ω−1 cm−1 and ∼0.93%, respectively, by one to two orders of magnitude larger than those of the typical 3d ferromagnetic oxides such as La0.67Sr0.33MnO3. Density functional theory calculations indicate the existence of avoid band crossings in the electronic band structure of the ferromagnetic CRO layer, which enhances Berry curvature thus strong anomalous Hall effects. Further evidences from polarized neutron reflectometry show that the CaRuO3 layers are in a fully ferromagnetic state (∼0.8 μB/Ru), in sharp contrast to the proximity-induced canted antiferromagnetic state in 5d oxides SrIrO3 and CaIrO3 (∼0.1 μB/Ir). More than that, the magnetic anisotropy of the (001)-(LaMnO3/CaRuO3) superlattices is eightfold symmetric, showing potential applications in the technology of multistate data storage.  相似文献   

3.
The structure of interfaces in superconducting/ferromagnetic YBa2Cu3O7−x/La0.67Ca0.33MnO3 superlattices has been analyzed by scanning transmission electron microscopy and high spatial resolution electron energy loss spectroscopy. Individual layers are flat over long lateral distances. The interfaces are coherent, free of defects, exhibiting no roughness, and are located at the BaO plane of the superconductor. Concerning chemical disorder, EELS measurements show the absence of measurable chemical interdiffusion within experimental error bars.  相似文献   

4.
The technique of metal organic chemical vapor deposi-tion has been used to prepare strained-layer superlattices in the GaAs + GaP system. The superlattices consist of alternating layers of GaP and GaAsxP1?x for x = 0.2 to 1.0, which vary in thickness from 30 to 400 Å. The layers were grown by the decomposition of trlmethylgallium and various mixtures of ASH3 and PH3 in H2 at 800δC. The thickness and uniformity of the layers were determined by optical and transmission electron microscopy and x-ray diffraction. The composition of the layers was determined from x-ray diffraction. A new analysis has been developed to determine the layer strain as well as the composition of thick layers (~ 300 Å). Transmission electron microscopy has been used to yield direct evidence that strained-layer superlattices can be used to remove the misfit dislocations generated during the epitaxial growth of a GaAsxP1-x alloy on a lattice mismatched GaP substrate. These results are in agreement with the previous work of Matthews and Blakeslee. Optical absorption, photocurrent spectroscopy and photoluminescence have been used to deter-mine the band gap energy as well as the energies for other optical transitions. The values are in excellent agreement with the values predicted by tight binding and effective mass calculations.  相似文献   

5.
In this work, Bi2Te3-Sb2Te3 superlattices were prepared by the nanoalloying approach. Very thin layers of Bi, Sb, and Te were deposited on cold substrates, rebuilding the crystal structure of V2VI3 compounds. Nanoalloyed super- lattices consisting of alternating Bi2Te3 and Sb2Te3 layers were grown with a thickness of 9 nm for the individual layers. The as-grown layers were annealed under different conditions to optimize the thermoelectric parameters. The obtained layers were investigated in their as-grown and annealed states using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive x-ray (EDX) spectroscopy, transmission electron microscopy (TEM), and electrical measurements. A lower limit of the elemental layer thickness was found to have c-orientation. Pure nanoalloyed Sb2Te3 layers were p-type as expected; however, it was impossible to synthesize p-type Bi2Te3 layers. Hence the Bi2Te3-Sb2Te3 superlattices consisting of alternating n- and p-type layers showed poor thermoelectric properties.  相似文献   

6.
The heat transport mechanisms in superlattices are identified from the cross‐plane thermal conductivity Λ of (AlN)x–(GaN)y superlattices measured by time‐domain thermoreflectance. For (AlN)4.1 nm–(GaN)55 nm superlattices grown under different conditions, Λ varies by a factor of two; this is attributed to differences in the roughness of the AlN/GaN interfaces. Under the growth condition that gives the lowest Λ, Λ of (AlN)4 nm–(GaN)y superlattices decreases monotonically as y decreases, Λ = 6.35 W m−1 K−1 at y = 2.2 nm, 35 times smaller than Λ of bulk GaN. For long‐period superlattices (y > 40 nm), the mean thermal conductance G of AlN/GaN interfaces is independent of y, G ≈ 620 MW m−2 K−1. For y < 40 nm, the apparent value of G increases with decreasing y, reaching G ≈ 2 GW m−2 K−1 at y < 3 nm. MeV ion bombardment is used to help determine which phonons are responsible for heat transport in short period superlattices. The thermal conductivity of an (AlN)4.1 nm–(GaN)4.9 nm superlattice irradiated by 2.3 MeV Ar ions to a dose of 2 × 1014 ions cm−2 is reduced by <35%, suggesting that heat transport in these short‐period superlattices is dominated by long‐wavelength acoustic phonons. Calculations using a Debye‐Callaway model and the assumption of a boundary scattering rate that varies with phonon‐wavelength successfully capture the temperature, period, and ion‐dose dependence of Λ.  相似文献   

7.
In spintronics, identifying an effective technique for generating spin‐polarized current has fundamental importance. The spin‐filtering effect across a ferromagnetic insulating layer originates from unequal tunneling barrier heights for spin‐up and spin‐down electrons, which has shown great promise for use in different ferromagnetic materials. However, the low spin‐filtering efficiency in some materials can be ascribed partially to the difficulty in fabricating high‐quality thin film with high Curie temperature and/or partially to the improper model used to extract the spin‐filtering efficiency. In this work, a new technique is successfully developed to fabricate high quality, ferrimagnetic insulating γ‐Fe2O3 films as spin filter. To extract the spin‐filtering effect of γ‐Fe2O3 films more accurately, a new model is proposed based on Fowler–Nordheim tunneling and Zeeman effect to obtain the spin polarization of the tunneling currents. Spin polarization of the tunneled current can be as high as ?94.3% at 2 K in γ‐Fe2O3 layer with 6.5 nm thick, and the spin polarization decays monotonically with temperature. Although the spin‐filter effect is not very high at room temperature, this work demonstrates that spinel ferrites are very promising materials for spin injection into semiconductors at low temperature, which is important for development of novel spintronics devices.  相似文献   

8.
2D layered 3‐rhombohedral (3R) phase transition metal dichalcogenides (TMDs) have received significantly increased research interest in nonlinear optical applications due to their unique crystal structures and broken inversion symmetry. However, controlled growth of 2D 3R phase TMDs still remains a great challenge. In this work, a direct growth of large‐area WS2 and WSe2 atomic layers with controllable crystal phases via a developed temperature selective physical vapor deposition route is reported. Large‐area triangular 3R phase layers are synthesized at a lower deposition temperature. Steady state and time‐resolved photoluminescence spectroscopy and Raman spectroscopy are used to study the unique properties of 3R phase layers due to different layer stacking and interlayer coupling. More importantly, with broken inversion symmetry, 3R phase layers show a quadratically increased second harmonic generation (SHG) intensity with respect to layer numbers. Furthermore, by polarization‐resolved SHG, a uniform polarization preference is observed in bilayer and trilayer 3R phase WS2, which could be a benefit for practical applications. The results not only contribute to the controlled growth of 2D TMDs layers with different phases but also pave the way to promising nonlinear optical devices.  相似文献   

9.
Single‐crystalline thin films of the homologous series InGaO3(ZnO)m (where m is an integer) are fabricated by the reactive solid‐phase epitaxy (R‐SPE) method. Specifically, the role of ZnO as epitaxial initiator layer for the growth mechanism is clarified. High‐temperature annealing of bilayer films consisting of an amorphous InGaO3(ZnO)5 layer deposited at room temperature and an epitaxial ZnO layer on yttria‐stabilized zirconia (YSZ) substrate allows for the growth of single‐crystalline film with controlled chemical composition. The epitaxial ZnO thin layer plays an essential role in determining the crystallographic orientation, while the ratio of the thickness of both layers controls the film composition.  相似文献   

10.
We performed the first-principles calculation to investigate the electronic structure and polarization behaviors in PbTiO3/SrTiO3 (PST) superlattices. The DOS (density of state) profiles show that there are strong hybridizations of atom Ti–O and Pb–O which play very important roles on ferroelectricity of the PbTiO3/SrTiO3 superlattices. Comparing to the corresponding paraelectric phase, we find the electrons of the PT (PbTiO3) layers occupy lower energy states and electrons of the ST (SrTiO3) layer occupy higher energy states. It is shown that the polarizations of the superlattices decrease with proportion of SrTiO3 increasing. The constant polarization of local layer indicates that PST superlattices with small modulation lengthen can be approximately considered as a single ferroelectric material. Furthermore, according to electrostatic model, we find that directions of internal electric fields in PT and ST layers are opposite. In PST superlattices, internal electric field in PT layer leads to the loss of polarization of this layer, but the polarization of ST layer is induced by internal electric field of this layer. Compared to the value of the polarization in bulk PbTiO3, polarization of PST is smaller.  相似文献   

11.
Graphitic carbon nitride (g‐C3N4) has been commonly used as photocatalyst with promising applications in visible‐light photocatalytic water‐splitting. Rare studies are reported in applying g‐C3N4 in polymer solar cells. Here g‐C3N4 is applied in bulk heterojunction (BHJ) polymer solar cells (PSCs) for the first time by doping solution‐processable g‐C3N4 quantum dots (C3N4 QDs) in the active layer, leading to a dramatic efficiency enhancement. Upon C3N4 QDs doping, power conversion efficiencies (PCEs) of the inverted BHJ‐PSC devices based on different active layers including poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PC61BM), poly(4,8‐bis‐alkyloxybenzo(l,2‐b:4,5‐b′)dithiophene‐2,6‐diylalt‐(alkyl thieno(3,4‐b)thiophene‐2‐carboxylate)‐2,6‐diyl):[6,6]‐phenyl C71‐butyric acid methyl ester (PBDTTT‐C:PC71BM), and poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐3‐fluorothieno [3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th):PC71BM reach 4.23%, 6.36%, and 9.18%, which are enhanced by ≈17.5%, 11.6%, and 11.8%, respectively, compared to that of the reference (undoped) devices. The PCE enhancement of the C3N4 QDs doped BHJ‐PSC device is found to be primarily attributed to the increase of short‐circuit current (Jsc), and this is confirmed by external quantum efficiency (EQE) measurements. The effects of C3N4 QDs on the surface morphology, optical absorption and photoluminescence (PL) properties of the active layer film as well as the charge transport property of the device are investigated, revealing that the efficiency enhancement of the BHJ‐PSC devices upon C3N4 QDs doping is due to the conjunct effects including the improved interfacial contact between the active layer and the hole transport layer due to the increase of the roughness of the active layer film, the facilitated photoinduced electron transfer from the conducting polymer donor to fullerene acceptor, the improved conductivity of the active layer, and the improved charge (hole and electron) transport.  相似文献   

12.
The local compositional heterogeneity associated with the short‐range ordering of Mg and Nb in PbMg1/3Nb2/3O3 (PMN) is correlated with its characteristic relaxor ferroelectric behavior. Fully ordered PMN is not prepared as a bulk material. This work examines the relaxor behavior in PMN thin films grown at temperatures below 1073 K by artificially reducing the degree of disorder via synthesis of heterostructures with alternate layers of Pb(Mg2/3Nb1/3)O3 and PbNbO3, as suggested by the random‐site model. 100 nm thick, phase‐pure films are grown epitaxially on (111) SrTiO3 substrates using alternate target timed pulsed‐laser deposition of Pb(Mg2/3Nb1/3)O3 and PbNbO3 targets with 20% excess Pb. Selected area electron diffraction confirms the emergence of (1/2, 1/2, 1/2) superlattice spots with randomly distributed ordered domains as large as ≈150 nm. These heterostructures exhibit a dielectric constant of 800, loss tangents of ≈0.03 and 2× remanent polarization of ≈11 µC cm?2 at room temperature. Polarization–electric field hysteresis loops, Rayleigh data, and optical second‐harmonic generation measurements are consistent with the development of ferroelectric domains below 140 K. Temperature‐dependent permittivity measurements demonstrate reduced frequency dispersion compared to short range ordered PMN films. This work suggests a continuum between normal and relaxor ferroelectric behavior in the engineered PMN thin films.  相似文献   

13.
ZnSe and ZnTe single-crystal layers have been grown onto (100) GaAs substrates by low-pressure metalorganic vapor-phase epitaxy (LP-MOVPE) using the triethylamine-dimethylzinc adduct [DMZn(NEt3)] as the zinc precursor. The selenium and tellurium precursors were H2Se (5% in H2) and di-isopropyltellurium (DiPTe), respectively. These two semiconductors have been grown with different VI/II molar ratios, at different growth temperatures, and with an overall growth pressure ranging from 40 to 400 Torr. Optimal growth parameters have been determined by optical means for the two materials. This information was then used to grow ZnTe/ZnSe strained-layer superlattices. We have studied structures grown on both ZnSe and ZnTe relaxed buffer layers which display a drastic dependence of the Stokes shift between photoluminescence and the optical bandgap on the nature of the buffer layer. Growth interruptions have been used to optimize the optical properties of the superlattices. Theoretical modeling of superlattice band structures has been performed using results of optical and structural characterizations. Observations of zone center transitions as well as excitons associated with the miniband dispersion of the superlattices are reported, in agreement with the theoretical calculation.  相似文献   

14.
The refractive indices of self‐assembled organic electro‐optic superlattices can be tuned by intercalating high‐Z optically transparent group 13 metal oxide sheets into the structures during the self‐assembly process. Microstructurally regular acentricity and sizable electro‐optic responses are retained in this straightforward synthetic procedure. This “one‐pot” all wet‐chemistry approach involves: i) layer‐by‐layer covalent self‐assembly of intrinsically acentric multilayers of high‐hyperpolarizability chromophores on inorganic oxide substrates, ii) protecting group cleavage to generate a large density of reactive surface hydroxyl sites, iii) self‐limiting capping of each chromophore layer with octachlorotrisiloxane, iv) deposition of metal oxide sheets derived from THF solutions of Ga(OiC3H7)3 or In(OiC3H7)3, and v) covalent capping of the resulting superlattices.  相似文献   

15.
The photoluminescence, transmittance, charge‐carrier recombination dynamics, mobility, and diffusion length of CH3NH3PbI3 are investigated in the temperature range from 8 to 370 K. Profound changes in the optoelectronic properties of this prototypical photovoltaic material are observed across the two structural phase transitions occurring at 160 and 310 K. Drude‐like terahertz photoconductivity spectra at all temperatures above 80 K suggest that charge localization effects are absent in this range. The monomolecular charge‐carrier recombination rate generally increases with rising temperature, indicating a mechanism dominated by ionized impurity mediated recombination. Deduced activation energies Ea associated with ionization are found to increase markedly from the room‐temperature tetragonal (Ea ≈ 20 meV) to the higher‐temperature cubic (Ea ≈ 200 meV) phase adopted above 310 K. Conversely, the bimolecular rate constant decreases with rising temperature as charge‐carrier mobility declines, while the Auger rate constant is highly phase specific, suggesting a strong dependence on electronic band structure. The charge‐carrier diffusion length gradually decreases with rising temperature from about 3 μm at ?93 °C to 1.2 μm at 67 °C but remains well above the optical absorption depth in the visible spectrum. These results demonstrate that there are no fundamental obstacles to the operation of cells based on CH3NH3PbI3 under typical field conditions.  相似文献   

16.
Transition‐metal oxides show genuine potential in replacing state‐of‐the‐art carbonaceous anode materials in lithium‐ or sodium‐ion batteries because of their much higher theoretical capacity. However, they usually undergo massive volume change, which leads to numerous problems in both material and electrode levels, such as material pulverization, instable solid‐electrolyte interphase, and electrode failure. Here, it is demonstrated that lithium‐ion breathable hybrid electrodes with 3D architecture tackle all these problems, using a typical conversion‐type transition‐metal oxide, Fe3O4, of which nanoparticles are anchored onto 3D current collectors of Ni nanotube arrays (NTAs) and encapsulated by δ‐MnO2 layers (Ni/Fe3O4@MnO2). The δ‐MnO2 layers reversibly switch lithium insertion/extraction of internal Fe3O4 nanoparticles and protect them against pulverizing and detaching from NTA current collectors, securing exceptional integrity retention and efficient ion/electron transport. The Ni/Fe3O4@MnO2 electrodes exhibit superior cyclability and high‐capacity lithium storage (retaining ≈1450 mAh g?1, ≈96% of initial value at 1 C rate after 1000 cycles).  相似文献   

17.
The formation of quantized energy states in ultrathin layers of indium oxide (In2O3) grown via spin coating and thermally annealed at 200 °C in air is studied. Optical absorption measurements reveal a characteristic widening of the optical band gap with reducing In2O3 layer thickness from ≈43 to ≈3 nm in agreement with theoretical predictions for an infinite quantum well. Through sequential deposition of In2O3 and gallium oxide (Ga­2O3) layers, superlattice‐like structures with controlled dimensionality and spatially varying conduction band characteristics are demonstrated. This simple method is then explored for the fabrication of functional double‐barrier resonant tunneling diodes. Nanoscale current mapping analysis using conductive atomic force microscopy reveals that resonant tunneling is not uniform but localized in specific regions of the apparent device area. The latter observation is attributed to variation in the layer(s) thickness of the In2O3 quantum well and/or the Ga2O3 barrier layers. Despite the nonidealities, the tremendous potential of solution‐processable oxide semiconductors for the development of quantum effect devices that have so far been demonstrated only via sophisticated growth techniques is demonstrated.  相似文献   

18.
Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al2O3 dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al2O3 dopant layer deposited during one ALD cycle could provide ≈4.5 × 1013 cm?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al2O3 layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.  相似文献   

19.
Dielectric energy‐storage capacitors have received increasing attention in recent years due to the advantages of high voltage, high power density, and fast charge/discharge rates. Here, a new environment‐friendly 0.76NaNbO3–0.24(Bi0.5Na0.5)TiO3 relaxor antiferroelectric (AFE) bulk ceramic is studied, where local orthorhombic Pnma symmetry (R phase) and nanodomains are observed based on high‐resolution transmission electron microscopy, selected area electron diffraction, and in/ex situ synchrotron X‐ray diffraction. The orthorhombic AFE R phase and relaxor characteristics synergistically contribute to the record‐high energy‐storage density Wrec of ≈12.2 J cm?3 and acceptable energy efficiency η ≈ 69% at 68 kV mm?1, showing great advantages over currently reported bulk dielectric ceramics. In comparison with normal AFEs, the existence of large random fields in the relaxor AFE matrix and intrinsically high breakdown strength of NaNbO3‐based compositions are thought to be responsible for the observed energy‐storage performances. Together with the good thermal stability of Wrec (>7.4 J cm?3) and η (>73%) values at 45 kV mm?1 up to temperature of 200 °C, it is demonstrated that NaNbO3‐based relaxor AFE ceramics will be potential lead‐free dielectric materials for next‐generation pulsed power capacitor applications.  相似文献   

20.
The mechanism of charge generation in transition metal oxide (TMO)‐based charge‐generation layers (CGL) used in stacked organic light‐emitting diodes (OLEDs) is reported upon. An interconnecting unit between two vertically stacked OLEDs, consisting of an abrupt heterointerface between a Cs2CO3‐doped 4,7‐diphenyl‐1,10‐phenanthroline layer and a WO3 film is investigated. Minimum thicknesses are determined for these layers to allow for simultaneous operation of both sub‐OLEDs in the stacked device. Luminance–current density–voltage measurements, angular dependent spectral emission characteristics, and optical device simulations lead to minimum thicknesses of the n‐type doped layer and the TMO layer of 5 and 2.5 nm, respectively. Using data on interface energetic determined by ultraviolet photoelectron and inverse photoemission spectroscopy, it is shown that the actual charge generation occurs between the WO3 layer and its neighboring hole‐transport material, 4,4',4”‐tris(N‐carbazolyl)‐triphenyl amine. The role of the adjacent n‐type doped electron transport layer is only to facilitate electron injection from the TMO into the adjacent sub‐OLED.  相似文献   

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