Emergent phenomena in manganites under spatial confinement

It is becoming increasingly clear that the exotic properties displayed by correlated electronic materials such as high- Tc superconductivity in cuprates, colossal magnetoresistance （CMR） in manganites, and heavy-fermion compounds are intimately related to the coexistence of competing nearly degenerate states which couple simultaneously active degrees of freedom---charge, lattice, orbital, and spin states. The striking phenomena associated with these materials are due in a large part to spatial electronic inhomogeneities, or electronic phase separation （EPS）. In many of these hard materials, the functionality is a result of the soft electronic component that leads to self-organization. In this paper, we review our recent work on a novel spatial confinement technique that has led to some fascinating new discoveries about the role of EPS in manganites. Using lithographic techniques to confine manganite thin films to length scales of the EPS domains that reside within them, it is possible to simultaneously probe EPS domains with different electronic states. This method allows for a much more complete view of the phases residing in a material and gives vital information on phase formation, movement, and fluctuation. Pushing this trend to its limit, we propose to control the formation process of the EPS using external local fields, which include magnetic exchange field, strain field, and electric field. We term the ability to pattern EPS ＂electronic nanofabrication.＂ This method allows us to control the global physical properties of the system at a very fundamental level, and greatly enhances the potential for realizing true oxide electronics.

Some Important Features of Manganites

Manganites are very complex systems because of interplay among charge, spin, orbital and lattice degrees of freedom. To come closer to the understanding of its nature, we discuss its three important features: 1) correlation between magnetization and electrical resistivity in the same temperature range;2) detection of chemical constitution and the arrangement of Mn3+ and Mn4+ ions at different hole concentrations;and 3) how electrical current flows through double exchange in manganites. The first feature will be discussed for three-dimensional manganies. The features 2 and 3 are inscrutable in three-dimensional manganites. So they will be discussed for one-dimensional manganites and then generalized. One-dimensional solid has been discussed because it may give a see-through picture of various aspects of manganites. All the discussions will be done through a representative example of La1-xCaxMnO3, because it is the intermediate bandwidth manganite;has been most widely investigated and has the highest magnetoresistance. If two things: 1) magnetization and resistivity as a function of temperature at various magnetic fields;and 2) phase diagrams of other manganites are known, their properties can be understood by the discussion of the three features mentioned above.

Nanoscale control of low-dimensional spin structures in manganites

Due to the upcoming demands of next-generation electronic/magnetoelectronic devices with low-energy consumption,emerging correlated materials（such as superconductors,topological insulators and manganites） are one of the highly promising candidates for the applications.For the past decades,manganites have attracted great interest due to the colossal magnetoresistance effect,charge-spin-orbital ordering,and electronic phase separation.However,the incapable of deterministic control of those emerging low-dimensional spin structures at ambient condition restrict their possible applications.Therefore,the understanding and control of the dynamic behaviors of spin order parameters at nanoscale in manganites under external stimuli with low energy consumption,especially at room temperature is highly desired.In this review,we collected recent major progresses of nanoscale control of spin structures in manganites at low dimension,especially focusing on the control of their phase boundaries,domain walls as well as the topological spin structures（e.g.,skyrmions）.In addition,capacitor-based prototype spintronic devices are proposed by taking advantage of the above control methods in manganites.This capacitor-based structure may provide a new platform for the design of future spintronic devices with low-energy consumption.

Electrical and Magnetic Properties of Bilayer Manganites La_(1.4)Sr_(1.6)Mn_(1.96)TE_(0.04)O_7 (TE=Mn, Fe, Ti, Nb)

The electrical and magnetic properties of bilayer manganites La1.4Sr1.6Mn1.96TE0.04O7（TE = Mn, Fe, Ti, Nb） were investigated. Doping caused obvious changes in electrical and magnetic behaviors such as decrease of insulator-metal transition and magnetic transition temperatures, increase of peak resistivity, and different magnetoresistance effect. These changes had a significant degree of correlation with the valence of doped ions. From Fe, Ti to Nb doping, the effect was doubly stronger. The results could be well understood by considering the different destructions on double-exchange interaction and different influences on lattice distortion caused by Fe, Ti and Nb doping. The temperature dependence of magnetization measured at high field showed that the influence of doping was greatest near three-dimensional magnetic transition temperature of parent phase.

High Temperature LFMR in Yttrium Doped Perovskite Manganites

Porous ceramic samples of Y doped perovskite manganites were prepared. In these samples, the transition from high temperature paramagnetic insulator to low temperature ferromagnetic metal as well as the low field magnetoresistance (LFMR) effect at the low temperature is similar to that in dense samples. Opposite to that in dense samples, LFMR effect in porous sample is observed at the high temperature close to the peak of MR T curves. The results suggest that the high temperature LFMR effect and the applicable colossal magnetoresistance (CMR) materials could be obtained by controlling the microstructures of this class of perovskite manganites.

Structural and Electrical Properties of Layered Pervoskite Manganites Nd_(2-2x)Sr_(1+2x)Mn_2O_7 (x=0.25, 0.3, 0.4)

Tetragonally layered perovskite manganites of Nd2-2xSr1＋2xMn2O7（x =0.25, 0.3, 0.4） were fabricated by using solid-state reaction technique. Structural characterization of the compounds was investigated by X-ray diffraction （XRD） and FT-IR absorption spectra. The XRD patterns revealed that all the samples were single phase. X-ray photoemission spectroscopy （XPS） was used to investigate their electronic structures. It was found that manganese was in mixed states of Mn^3＋ and Mn^4＋ whereas lattice oxygen and chemical absorbed oxygen were existed in all the samples. The high temperature electrical properties of Nd2-2xSr1＋2xMn2O7 （x = 0.3, 0.4） were measured by standard four-probe technique. The results showed that both compounds had semi-conductivity behavior in the temperature range of 300 - 1073 K, and the electrical conduction was dominated by thermally activated behavior above 500 K.

Colossal magnetoresistance in manganites and related prototype devices

We review colossal magnetoresistance in single phase manganites, as related to the field sensitive spin-charge interactions and phase separation; the rectifying property and negative/positive magnetoresistance in manganite/Nb：SrTio3 p-n junctions in relation to the special interface electronic structure; magnetoelectric coupling in manganite/ferroelectric structures that takes advantage of strain, carrier density, and magnetic field sensitivity; tunneling magnetoresistance in tunnel junctions with dielectric, ferroelectric, and organic semiconductor spacers using the fully spin polarized nature of manganites; and the effect of particle size on magnetic properties in manganite nanoparticles.

Structural and magnetic properties of La_(0.7)Sr_(0.1)Ag_xMnO_(3-δ) perovskite manganites

Ag-doped manganite powder samples, La0.7Sr0.1AgxMnO3 6 （x = 0.00, 0.025, 0.05, 0.075, and 0.10） were synthesized using the sol-gel method. X-ray diffraction patterns indicated that the samples had two phases with the R-3c perovskite being the dominant phase and Mn3O4 being the second phase. X-ray energy dispersive spectra indicated that the ratio of Ag to La was very close to that of the nominal composition in the samples. The specific saturation magnetizations at 300 K increased from 32.0 A.mZ/kg when x = 0.00 to 46.8 A-mZ/kg when x = 0.10. The Curie temperature, TC, of the samples increased from 310 K when x = 0.00 to 328 K when x = 0.10. Because the atomic concentration ratios of La, Sr, and Mn in the five samples were all the same and only the Ag concentration changed, the variations of the specific saturation magnetizations at 300 K and the Curie temperatures suggested that the Ag cations have been doped into the A sites of the perovskite phase in the samples.

Transport-magnetism Correlation and Colossal Magnetoresistance in Mixed-valent Manganites

A phenomenological model based on phase separation between ferromagnetic metallic and paramagnetic insulating domains was applied to analyze the electrical transport and colossal magnetoresistance for mixed-valent manganites of RE_(2/3)AE_(1/3)MnO_3. The results show that the model can yield results in agreement with experimental observations in these manganites. The present approach provides a simple picture to visualize the reason that the temperature dependence of resistance (with and without applied magnetic fields) in these compounds has the peculiar shape, without invoking any complicated concept.

Magnetic and electronic properties of La-doped hexagonal 4H-SrMnO_(3)

As typical strongly correlated electronic materials, manganites show rich magnetic phase diagrams and electronic structures depending on the doped carrier density. Most previous relevant studies of doped manganites rely on the cubic/orthorhombic structures, while the hexagonal structure is much less studied. Here first-principles calculations are employed to investigate the magnetic and electronic structures of La-doped 4H-SrMnO_(3). By systematically analyzing the two kinds of La-doped positions, our calculations predict that the doped electron with lattice distortion would prefer to form polarons, which contribute to the local magnetic phase transition, nonzero net magnetization, and semiconducting behavior. In addition, the energy gap decreases gradually with increasing doping concentration, indicating a tendency of insulator–metal transition.

Magnetoresistive properties of Ni-doped La_(0.7)Sr_(0.3)MnO_3 manganites

Lao.7Sr0.3Mnl_xNixO3 （x = 0, 0.025, 0.050 and 0.075） ceramics were prepared by the conventional solid-state reaction method. The partial substitution of Mn by Ni2＋ leads to a decrease in cell volume as well as a structural transition from the rhombohedral to the orthorhombic structure. Ni2＋ doping increases the electrical resistivity, decreases the semiconductor-metal transition temperature （Tms） and relatively enhances the room temperature magnetoresistance （MR）, especially in x = 0.025 and around Tins. With respect to conduction mechanism, the small polaron hopping （SPH） and the variable range hopping （VRH） models were used to ex- amine conduction in the semiconducting region.

Elastic properties of double layered manganites R_(1.2)Sr_(1.8)Mn_2O_7(R=La, Pr, Nd, Sm)

The polycrystalline colossal magnetoresistive double-layered manganite samples R1.2Sr1.8Mn2O7（R = La Pr, Nd, Sm） were prepared by the sol–gel method and their room temperature elastic behavior was investigated by ultrasonic pulse transmission technique at 1 MHz. The values of elastic constants were calculated from longitudinal and shear velocities and they were corrected to zero porosity using Hasselman and Fulrath＇s formulae. The elastic constants of the samples were also estimated by Modi＇s heterogeneous metal-mixture rule which is based on the metal ions present in the samples. The measured,corrected, and estimated values of elastic moduli are found to increase with decreasing rare earth ion size. The variation of elastic moduli with the size of the rare earth ion is interpreted in terms of strength of interatomic bonding.

High-temperature synthesis and electronic bonding analysis of Ca-doped LaMnO_(3) rare-earth manganites

Doped lanthanum manganites La_(1-x)Ca_(x)MnO_(3) with five different concentrations of Ca(x=0.1,0.2,0.3,0.4 and 0.5) were synthesized by high-temperature solidstate reaction method and characterized.The prepared samples were experimentally analyzed by X-ray diffraction(XRD),ultraviolet-visible spectroscopy(UV-Vis),scanning electron microscopy/energy dispersive spectroscopy(SEM/EDS) and vibrating sample magnetometer(VSM)measurements.Orthorhombic structure is confirmed for this compound from powder X-ray diffraction data.The XRD data confirm the shrinkage in the unit cell of synthesized samples for increasing calcium concentration.The UV-Visible analysis for the estimation of optical band gap(E_(g)) reveals that the band gap decreases with the incorporation of Ca.The synthesized samples were investigated for charge density distribution using maximum entropy method,utilizing the XRD data sets.From the charge density analysis,it is found that the bond lengths for La-O and Mn-O bonds decrease with the addition of Ca.The ionic nature between La and O atoms and covalent nature between Mn and O atoms are enhanced for 40% of calcium-doping.For 50% of Ca-doped sample,ionic nature between La and O atoms and covalent nature between Mn and O atoms decrease.All the prepared samples exhibit ferromagnetism at 20 K and paramagnetism at 300 K.

Nanomaterials Synthesis and Effect of Granular Disorders on Electrical Behavior of Lanthanum Manganites

Comprehensive investigation on the synthesis and electrical transport behaviors of polycrystalline samples of lanthanum manganite due to static disorder was reported. The process parameters were optimized for different batches to yield variable grain sizes. Different sintering conditions and technique like thermal cycling were employed to obtain better grain packing density. The liquid nitrogen and air quenching of the samples were carried out to restrict the grain growth with well defused grain boundary. Variable grain habits and sizes were synthesized by standard solid-state reaction and modified sol-gel synthesis routes. Large variation of grain size, connectivity and packing was observed by varying sintering temperature and synthesis technique. The process dependent grain sizes were observed in the wide range from 20 nm to 1.5 μm by transmission and scanning electron microscopy, The variations in residual resistivity as well as metal-insulator transitions are observed. The observed data were analyzed on the basis of contributions from various dynamic interactions and static disorders.

Effect of Ag substitution on structural,magnetic and magnetocaloric properties of Pr_(0.6)Sr_(0.4–x)Ag_xMnO_3 manganites

A systematic investigation on the structural, magnetic and magnetocaloric properties of Pr_（0.6）Sr_（0.4-x）Ag_xMnO_3（x=0.05 and 0.1） manganites was reported. Rietveld refinements of the X-ray diffraction patterns confirmed that all samples were single phase and crystallized in the orthorhombic structure with Pnma space group. Magnetic measurements in a magnetic applied field of 0.01T revealed that the ferromagnetic-paramagnetic transition temperature T_C decreased from about 293 to 290 K with increasing silver content from x=0.05 to 0.1. The reported magnetocaloric entropy change and relative cooling power for both samples were considerably remarkable with a △S_（max） value of 1.9 J/（kg·K）and maximum RCP values of 100 J/kg, under a magnetic field change（？μ0H） equal to 1.8T. The analysis of the universal curves gave an evidence of a second order magnetic transition for the studied samples. The magnetic field influence on both the magnetic entropy change and the relative cooling power was also studied and discussed.

A-site ordered state in manganites with perovskite-like structure based on optimally doped compounds Ln0.70Ba0.30MnO3（Ln=Pr,Nd）

In this paper,we report on the crystal structure and magnetic properties of the nano structured Baordered phases of rare-earth manganites obtained from the optimally doped solid solutions Ln0.70Ba0.30MnO3(Ln=Pr,Nd).The materials were studied by X-ray diffraction,scanning electron microscopy,energy dispersive spectroscopy and SQUID-magnetometry techniques.It is found that states with different degrees of cation ordering in the A-sublattice of the ABO3 perovskite can be obtained by employing special conditions of chemical treatment.In particular,reduction of the parent compounds results in the formation of a nanocomposite containing ferrimagnetic anion-deficient ordered phase LnBaMn2O5.Oxidation of the composite does not change an average size of the nanocrystallites,but drastically alters their phase composition to stabilize ferromagnetic stoichiometric ordered phase LnBaMn2O6 and ferromagnetic superstoichiometric disordered phase Ln0.90Ba0.10MnO3+δ.It is shown that the magnetic properties of the materials are determined by the joint action of chemical(cation ordering)and external(surface tension)pressures.

Negative Magnetism in Perovskite Manganites Gd1-xSrxMnO3（0.1 ≤x≤0.3）

A series of Sr-substituted Gd1-xSrxMnO3（0.1 ≤x≤0.3） materials was prepared via a standard method involving solid-state reaction. Their crystal structure within the entire doping region was determined to be orthorhombic perovskite type. The magnetic properties of the perovskite Gd1-xSrxMnO3（0.1 ≤x≤0.3） were thoroughly investigated. It appears that Mn ions with high valence state can induce stronger magnetization, and negative magnetization is evident in the manganites with x=0.1 and x=0.2, suggesting that valence fluctuation plays an important role in such systems. The result of XPS analysis indicates that the valence state of Mn ions is 3.25 and there seems to be excess amounts of oxygen in the structure of Gd0.8Sr0.2MnO3＋δ. In addition, the results of magnetization measurements demonstrate that spin reversal occurs only when the applied field is less than 1.99× 10^5 A/m, which presumably could be due to the negative exchange interaction between Mn sub-lattice and Gd sites.

Lattice Effects in La-Sm-Ca-Mn-O

The doping effects of Sm in La 0.67 Ca 0.33 MnO 3 oxide were studied. The results show that with increasing the doping amount of Sm the phase transition temperature of metal insulator for the materials decreases monotonically, the corresponding peak resistance increases rapidly, the Curie temperature decreases monotonically, and the magneto resistance ratio increases quickly. The effects of Sm doping can be explained in terms of lattice effects.

Electric and magnetic behaviour in double doped La2/3＋4x/3Sr1/3-4x/3Mn1-xMgxO3

The double-doped La2/3＋4x/3Sr1/3-4x/3Mn1-xMgxO3 samples with fixed Mn^3＋/Mn^4＋ ratio equal to 2/1 are investigated by means of magnetism and transport measurements. Phase separation is observed at temperature higher than T^onset c for x = 0.10 and 0.15. For x = 0.10, rather strong phase separation induces drastic magnetic random potential and results in the localization of carriers. Thus, the varlable-range hopping process dominates. For other samples, there is no or only weak phase separation above T^onset c. Thus, thermal activation mechanism is responsible for the high temperature transport behaviour. For x = 0.20 and 0.25, unexpected AFM behaviour is observed at low temperature. All these results are well understood by considering the special role of the ＂double-doping＂.

Transport and Magnetic Properties of Nanosized La_(0.6)Sm_(0.1)Sr_(0.3)MnO_3+xCoO Composites

The composites La0.6Sm0. 1Sr0.3MnO3 ＋ x CoO （x = 0.0, 0.1, 0.2, 0.3, 0.4 mol）, named as A x samples, were synthesized by the sol-gel technique to derive homogeneous CoO-coated composites. CoO addition induces an increase of resistivity （ρ） and a decrease of Curie temperature （TC）, magnetization, and Tpat which the p peak is located. It has been concluded that the resistivity below Tp fits well with the equation ρ = ρ0 ＋ ρ2 T^2 ＋ ρ4.5 T^4.5, indicating the importance of grain/domain boundary effects, the electron-electron scattering process, and the two magnon scattering process. On the other hand, the paramagnetic insulating region may be explained by using adiabatic small polaron hopping mechanism, thereby indicating that polaron hopping might be responsible for the conduction mechanism. Magnetoresistance results were explained by a two-level model of tunneling MR and percolation model.