H. Kuang

Giant negative thermal expansion in bonded MnCoGe-based compounds with Ni2In-type hexagonal structure.

MnCoGe-based compounds undergo a giant negative thermal expansion (NTE) during the martensitic structural transition from Ni2In-type hexagonal to TiNiSi-type orthorhombic structure. High-resolution neutron diffraction experiments revealed that the expansion of unit cell volume can be as large as ΔV/V ∼ 3.9%. The optimized compositions with concurrent magnetic and structural transitions have been studied for magnetocaloric effect. However, these materials have not been considered as NTE materials partially due to the limited temperature window of phase transition. The as-prepared MnCoGe-based compounds are quite brittle and naturally collapse into powders. By using a few percents (3-4%) of epoxy to bond the powders, we introduced residual stress in the bonded samples and thus realized the broadening of structural transition by utilizing the specific characteristics of lattice softening enforced by the stress. As a result, giant NTE (not only the linear NTE coefficient α but also the operation-temperature window) has been achieved. For example, the average α̅ as much as -51.5 × 10(-6)/K with an operating temperature window as wide as 210 K from 122 to 332 K has been observed in a bonded MnCo0.98Cr0.02Ge compound. Moreover, in the region between 250 and 305 K near room temperature, the α value (-119 × 10(-6)/K) remains nearly independent of temperature. Such an excellent performance exceeds that of most other materials reported previously, suggesting it can potentially be used as a NTE material, particularly for compensating the materials with large positive thermal expansions.

Abnormal percolative transport and colossal electroresistance induced by anisotropic strain in (011)-Pr 0.7 (Ca 0.6 Sr 0.4 ) 0.3 MnO 3 / PMN-PT heterostructure

Abnormal percolative transport in inhomogeneous systems has drawn increasing interests due to its deviation from the conventional percolation picture. However, its nature is still ambiguous partly due to the difficulty in obtaining controllable abnormal percolative transport behaviors. Here, we report the first observation of electric-field-controlled abnormal percolative transport in (011)-Pr0.7(Ca0.6Sr0.4)0.3MnO3/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 heterostructure. By introducing an electric-field-induced in-plane anisotropic strain-field in a phase separated PCSMO film, we stimulate a significant inverse thermal hysteresis (~ -17.5 K) and positive colossal electroresistance (~11460%), which is found to be crucially orientation-dependent and completely inconsistent with the well accepted conventional percolation picture. Further investigations reveal that such abnormal inverse hysteresis is strongly related to the preferential formation of ferromagnetic metallic domains caused by in-plane anisotropic strain-field. Meanwhile, it is found that the positive colossal electroresistance should be ascribed to the coactions between the anisotropic strain and the polarization effect from the poling of the substrate which leads to orientation and bias-polarity dependencies for the colossal electroresistance. This work unambiguously evidences the indispensable role of the anisotropic strain-field in driving the abnormal percolative transport and provides a new perspective for well understanding the percolation mechanism in inhomogeneous systems.

Anisotropic modulation of magnetic properties and the memory effect in a wide-band (011)-Pr 0.7 Sr 0.3 MnO 3 /PMN-PT heterostructure

Memory effect of electric-field control on magnetic behavior in magnetoelectric composite heterostructures has been a topic of interest for a long time. Although the piezostrain and its transfer across the interface of ferroelectric/ferromagnetic films are known to be important in realizing magnetoelectric coupling, the underlying mechanism for nonvolatile modulation of magnetic behaviors remains a challenge. Here, we report on the electric-field control of magnetic properties in wide-band (011)-Pr0.7Sr0.3MnO3/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 heterostructures. By introducing an electric-field-induced in-plane anisotropic strain field during the cooling process from room temperature, we observe an in-plane anisotropic, nonvolatile modulation of magnetic properties in a wide-band Pr0.7Sr0.3MnO3 film at low temperatures. We attribute this anisotropic memory effect to the preferential seeding and growth of ferromagnetic (FM) domains under the anisotropic strain field. In addition, we find that the anisotropic, nonvolatile modulation of magnetic properties gradually diminishes as the temperature approaches FM transition, indicating that the nonvolatile memory effect is temperature dependent. By taking into account the competition between thermal energy and the potential barrier of the metastable magnetic state induced by the anisotropic strain field, this distinct memory effect is well explained, which provides a promising approach for designing novel electric-writing magnetic memories.

Ultra-low thermal expansion realized in giant negative thermal expansion materials through self-compensation

Materials with zero thermal expansion (ZTE) or precisely tailored thermal expansion are in urgent demand of modern industries. However, the overwhelming majority of materials show positive thermal expansion. To develop ZTE or negative thermal expansion (NTE) materials as compensators has become an important challenge. Here, we present the evidence for the realization of ultra-low thermal expansion in Mn–Co–Ge–In particles. The bulk with the Ni2In-type hexagonal structure undergoes giant NTE owing to a martensitic magnetostructural transition. The major finding is that the thermal expansion behavior can be totally controlled by modulating the crystallinity degree and phase transition from atomic scale. Self-compensation effect leads to ultra-low thermal expansion with a linear expansion coefficient as small as +0.68 × 10−6/K over a wide temperature range around room temperature. The present study opens an avenue to reach ZTE particularly from the large class of giant NTE materials based on phase transition.

Negative thermal expansion and magnetocaloric effect in Mn-Co-Ge-In thin films

MnCoGe-based alloys with magnetostructural transition show giant negative thermal expansion (NTE) behavior and magnetocaloric effects (MCEs) and thus have attracted a lot of attention. However, the drawback of bad mechanical behavior in these alloys obstructs their practical applications. Here, we report the growth of Mn-Co-Ge-In films with thickness of about 45 nm on (001)-LaAlO3, (001)-SrTiO3, and (001)-Al2O3 substrates. The films grown completely overcome the breakable nature of the alloy and promote its multifunctional applications. The deposited films have a textured structure and retain first-order magnetostructural transition. NTE and MCE behaviors associated with the magnetostructural transition have been studied. The films exhibit a completely repeatable NTE around room temperature. NTE coefficient α can be continuously tuned from the ultra-low expansion (α ∼ −2.0 × 10−7/K) to α ∼ −6.56 × 10−6/K, depending on the growth and particle size of the films on different substrates. Moreover, the films e...

Magnetic properties of (misch metal, Nd)-Fe-B melt-spun magnets

The effect of replacing Nd with misch metal (MM) on magnetic properties and thermal stability has been investigated on melt-spun (Nd1-xMMx)13.5Fe79.5B7 ribbons by varying x from 0 to 1. All of the alloys studied crystallize in the tetragonal 2:14:1 structure with single hard magnetic phase. Curie temperature (Tc), coercivity (Hcj), remanence magnetization (Br) and maximum energy product ((BH)max) all decrease with MM content. The melt-spun MM13.5Fe79.5B ribbons with high ratio of La and Ce exhibit high magnetic properties of Hcj = 8.2 kOe and (BH)max= 10.3 MGOe at room temperature. MM substitution also significantly strengthens the temperature stability of coercivity. The coercivities of the samples with x = 0.2 and even 0.4 exhibit large values close to that of Nd13.5Fe79.5B7 ribbons above 400 K.

Gate control of ferromagnetic insulating phase in lightly-doped La0.875Sr0.125MnO3−δ film

The electric field effect on the lightly doped La0.875Sr0.125MnO3−δ (LSMO) thin film in electric double-layer transistors was investigated by measuring transport properties of the film under various gate voltages. It was found that the positive gate bias leads to an increase of the charge-orbital ordering (COO) transition temperature and a decrease of the Curie temperature TC, indicating the suppression of ferromagnetic metal (FMM) phases and preference of COO/ferromagnetic insulator (FMI) with the hole depletion by gate bias. Such different electric field effects can be ascribed to the weakening of the ferromagnetic interaction and enhancement of Jahn-Teller (JT) distortion caused by the transformation of JT inactive Mn4+-ions to JT active Mn3+-ions. Moreover, a step-like increase in the high temperature region of the ρ-T curve, which is related to the transition of cooperative JT distortion, was found to develop with increasing the positive bias, indicating that the cooperative JT distorted phase is sta...

The modulation of oxygen vacancies by the combined current effect and temperature cycling in La0.7Sr0.3CoO3 film

Modulating the oxygen defect concentration has been accepted as an effective method to obtain high catalytic activity in perovskite cobaltites. However, controllably modifying the oxygen vacancy is still a challenge in this type of materials, which strongly obstructs their application. Here, we report a successful oxygen vacancies modulation in the La0.7Sr0.3CoO3 (LSCO) film by using combined current effect and temperature cycling. The temperature dependent transport properties of the LSCO/LAO film were investigated. The results revealed that the resistance of the film keeps increasing under the repeated measurements. It was found that the accumulation of the oxygen vacancy by current effect transforms the Co4+ ion into Co3+ ion, which results in the enhancement of the resistance and thus the transport switching behavior. Moreover, the resistance in the cooling process was found to be much higher than that in previous cooling and heating processes, which indicates that the oxygen escapes more quickly in t...

Enhanced Field Modulation Sensitivity and Anomalous Polarity-Dependency Emerged in Spatial-Confined Manganite Strips

An anomalous polarity-dependent electrostatic field modulation effect, facilitated by spatial confinement, is found in an oxide-based field-effect prototype device with a spatial-confined Pr0.7(Ca0.6Sr0.4)0.3MnO3 channel. It is revealed that the dominant field modulation mode under a small bias field varies from a polarity-independent strain-mediated one to a nonvolatile polarity-dependent one with enhanced modulation sensitivity as the channel width narrows down to several micrometers. Specially, in the structure confined to length scales similar to that of the phase domains, the field modulation exhibits a greatly increased modulation amplitude around the transition temperature and an anomalous bias-polarity dependence that is diametrically opposite to the normal one observed in regular polarization field-effect. Further simulations show that a large in-plane polarization field is unexpectedly induced by a small out-of-plane bias field of 4 kV/cm in the narrow strip (up to 790 kV/cm for the 3 μm strip). Such large in-plane polarization field, facilitated and enhanced by size reduction, drives phase transitions in the narrow channel film, leading to the reconfiguration of percolation channel and nonvolatile modulation of transport properties. Accordingly, the accompanied polarity relationship between the induced in-plane polarization field and the applied vertical bias field well explains the observed anomalous polarity-dependence of the modulation. Our studies reveal a new acting channel in the nanoscale control of lateral configurations of electronic phase separation and macroscopic behaviors by a small vertical electric bias field in spatial-confined field-effect structures. This distinct acting mechanism offers new possibilities for designing low-power all-oxide-based electronic devices and exploiting new types of multifunctionality to other strongly correlated materials where electronic phase competition exists.

Electric field control of the small-polaron hopping conduction in spatial confined Pr0.7(Ca0.6Sr0.4)0.3MnO3/PMN-PT heterostructure

The electric field dependent high-temperature small-polaron hopping conduction was investigated in patterned Pr0.7(Ca0.6Sr0.4)0.3MnO3 strips. The small-polaronic activation energy EA and the carrier localization were found to decrease with the reduction of the strip size. Meanwhile, a similar dependence on the strip size was also obtained for the calculated small-polaron coupling constants, which could be related to the strain relaxation in strips. These results indicate that the spatial confinement prefers to delocalize the carrier and reduce the electron-phonon interaction. Furthermore, opposite variation trends of EA under negative and positive electric field were found in the strips with small size, which could be attributed to the enhancement of polarization effect induced by the reduction of strip size.