Shen Bao-Gen

Resistance switching in oxides with inhomogeneous conductivity

Electric-field-induced resistance switching (RS) phenomena have been studied for over 60 years in metal/dielectrics/metal structures. In these experiments a wide range of dielectrics have been studied including binary transition metal oxides, perovskite oxides, chalcogenides, carbon- and silicon-based materials, as well as organic materials. RS phenomena can be used to store information and offer an attractive performance, which encompasses fast switching speeds, high scalability, and the desirable compatibility with Si-based complementary metal—oxide—semiconductor fabrication. This is promising for nonvolatile memory technology, i.e., resistance random access memory (RRAM). However, a comprehensive understanding of the underlying mechanism is still lacking. This impedes faster product development as well as accurate assessment of the device performance potential. Generally speaking, RS occurs not in the entire dielectric but only in a small, confined region, which results from the local variation of conductivity in dielectrics. In this review, we focus on the RS in oxides with such an inhomogeneous conductivity. According to the origin of the conductivity inhomogeneity, the RS phenomena and their working mechanism are reviewed by dividing them into two aspects: interface RS, based on the change of contact resistance at metal/oxide interface due to the change of Schottky barrier and interface chemical layer, and bulk RS, realized by the formation, connection, and disconnection of conductive channels in the oxides. Finally the current challenges of RS investigation and the potential improvement of the RS performance for the nonvolatile memories are discussed.

Great magnetic entropy change in La(Fe, M)13 (M=Si, Al) with Co doping*

Very large magnetic entropy change ?SM, which originates from a fully reversible second-order transition at Curie temperature TC, has been discovered in compounds La(Fe, Si)13, La(Fe, Al)13 and those with Co doping. The maximum change ?SM ? 19 J?kg-1?K-1, achieved in LaFe11.4Si1.6 at 209K upon a 5T magnetic field change, exceeds that of Gd by more than a factor of 2. The TC of the Co-doped compounds shifts to higher temperatures. ?SM still has a considerable large magnitude near room temperature. The phenomena of very large ?SM, convenience of adjustment of TC, and also the superiority of low cost, strongly suggest that the compounds La(Fe, M)13 (M=Si, Al) with Co doping are suitable candidates for magnetic refrigerants at high temperatures.

Magnetic properties and magnetocaloric effects in NaZn13-type La(Fe, Al)13-based compounds

In this article, our recent progress concerning the effects of atomic substitution, magnetic field, and temperature on the magnetic and magnetocaloric properties of the LaFe13 xAlx compounds are reviewed. With an increase of the aluminum content, the compounds exhibit successively an antiferromagnetic (AFM) state, a ferromagnetic (FM) state, and a mictomagnetic state. Furthermore, the AFM coupling of LaFe13 xAlx can be converted to an FM one by substituting Si for Al, Co for Fe, and magnetic rare-earth R for La, or introducing interstitial C or H atoms. However, low doping levels lead to FM clusters embedded in an AFM matrix, and the resultant compounds can undergo, under appropriate applied fields, first an AFM‐FM and then an FM‐AFM phase transition while heated, with significant magnetic relaxation in the vicinity of the transition temperature. The Curie temperature of LaFe13 xAlx can be shifted to room temperature by choosing appropriate contents of Co, C, or H, and a strong magnetocaloric effect can be obtained around the transition temperature. For example, for the LaFe11:5Al1:5C0:2H1:0 compound, the maximal entropy change reaches 13.8 J kg 1 K 1 for a field change of 0‐5 T, occurring around room temperature. It is 42% higher than that of Gd, and therefore, this compound is a promising room-temperature magnetic refrigerant.In this article, our recent progresses about the effects of atomic substitution, magnetic field and temperature on the magnetic and magnetocaloric properties of the LaFe13-xAlx compounds are reviewed. With the increase of aluminum content, the compounds exhibit successively an antiferromagnetic (AFM), a ferromagnetic (FM), and a mictomagnetic state. Furthermore, the AFM coupling of LaFe13-xAlx can be converted to a FM coupling by substituting Si for Al, Co for Fe and magnetic rare-earth R for La, or introducing interstitial C or H atom. However, low doping levels lead to FM clusters embedded in AFM matrix, and the resultant compounds can undergo, under appropriate applied fields, first an AFM-FM and then a FM-AFM phase transition while heated, with significant magnetic relaxation in the vicinity of the transition temperature. The Curie temperature of LaFe13-xAlx can be shifted to room temperature by choosing appropriate contents of Co, C or H, and strong magnetocaloric effect can be obtained around the transition temperature. For example, for the LaFe11.5Al1.5C0.2H1.0 compound, the maximal entropy change reaches 13.8 J/kg K for a field change of 0-5 T, occurring around the room temperature. It is 42% higher than that of Gd and, therefore, this compound is a promising room-temperature magnetic refrigerant.

Large magnetic entropy change near room temperature in the LaFe11.5Si1.5H1.3 interstitial compound

The LaFe11.5Si1.5H1.3 interstitial compound has been prepared. Its Curie temperature TC (288 K) has been adjusted to around room temperature and the maximal magnetic entropy change (|?S|~17.0 J?kg-1?K-1 at TC) is larger than that of Gd (|?S|~9.8 J?kg-1?K-1 at TC=293 K) by ~73.5% under a magnetic change from 0 to 5 T. The origin of the large magnetic entropy change is attributed to the first-order field-induced itinerant-electron metamagnetic transition. Moreover, the magnetic hysteresis of LaFe11.5Si1.5H1.3 under the increase and decrease of the field is very small, which is favourable to magnetic refrigeration application. The present study suggests that the LaFe11.5Si1.5H1.3 compound is a promising candidate as a room-temperature magnetic refrigerant.

Structure, magnetic properties and giant magnetoresistance of YMn6Sn6-xGax (x=0-0.6) compounds

Structure, magnetic and transport properties of YMn6Sn6-xGax (0≤x≤0.6) compounds with a HfFe6Ge6-type structure were investigated. It was found that the Ga substitution leads to a contraction of the unit-cell volume. A transition from an antiferromagnetic to a ferromagnetic (or ferrimagnetic) state can be observed for samples (0.1≤x≤0.2) with increasing temperature. The antiferro-ferromagnetic transition for samples with x≤0.2 can also be induced by an external field. The required field is very low and decreases with increasing Ga concentration. More Ga concentration (x≥0.3) leads to the samples being ferromagnetic in the whole temperature range below the Curie temperature. The Ga substitution weakens the interlayer magnetic coupling between the Mn spins. Corresponding to the metamagnetic transition, a magnetoresistance as large as 32% under a field of 5 T was observed at 5 K for the sample with x=0.2.

Effect of R substitution on magnetic properties and magnetocaloric effects of La1-xRxFe11.5Si1.5 compounds with R=Ce, Pr and Nd

Magnetic properties and magnetocaloric effects of La1−xRxFe11.5Si1.5 (R = Pr, (0 ≤ x ≤ 0.5); R = Ce and Nd, (0 ≤ x ≤ 0.3)) compounds are investigated. Partially replacing La with R = Ce, Pr and Nd in La1−xRxFe11.5Si1.5 leads to a reduction in Curie temperature due to the lattice contraction. The substitution of R for La causes an enhancement in field-induced itinerant electron metamagnetic transition, which leads to a remarkable increase in magnetic entropy change ΔSm and also in hysteresis loss. However, a high effective refrigerant capacity RCeff is still maintained in La1−xRxFe11.5Si1.5. In the present samples, a large ΔSm and a high RCeff have been achieved simultaneously.

Magnetic properties and magnetocaloric effects of Mn5Ge3−xGax

We report on the magnetic properties and magnetocaloric effects of Mn5Ge3−xGax compounds with x=0.1, 0.2, 0.3, 0.4, 0.6 and 0.9. All samples crystallize in the hexagonal Mn5Si3-type structure with space group P63/mcm and order ferromagnetically. The Curie temperature of these compounds decreases with increasing x, from 306K (x=0.1) to 274K (x=0.9). The average Mn magnetic moments increases with increasing Ga content, reaching a maximum value at x=0.6. The magnetic entropy changes in these compounds are determined from the temperature and field dependence of the magnetization using the thermodynamic Maxwell relation. The Ga substitution has two kinds of influence on the magnetocaloric effect (MCE) of Mn5Ge3. One is that the magnitude of the magnetic entropy change decreases, the other is that the MCE peak becomes broadened.

Magnetic entropy change involving martensitic transition in NiMn-based Heusler alloys

Our recent progress on magnetic entropy change (ΔS) involving martensitic transition in both conventional and metamagnetic NiMn-based Heusler alloys is reviewed. For the conventional alloys, where both martensite and austenite exhibit ferromagnetic (FM) behavior but show different magnetic anisotropies, a positive ΔS as large as 4.1 Jkg−1 K−1 under a field change of 0–0.9 T was first observed at martensitic transition temperature TM ~ 197 K. Through adjusting the Ni:Mn:Ga ratio to affect valence electron concentration e/a, TM was successfully tuned to room temperature, and a large negative ΔS was observed in a single crystal. The −ΔS attained 18.0 Jkg−1K−1 under a field change of 0–5 T. We also focused on the metamagnetic alloys that show mechanisms different from the conventional ones. It was found that post-annealing in suitable conditions or introducing interstitial H atoms can shift the TM across a wide temperature range while retaining the strong metamagnetic behavior, and hence, retaining large magnetocaloric effect (MCE) and magnetoresistance (MR). The melt-spun technique can disorder atoms and make the ribbons display a B2 structure, but the metamagnetic behavior, as well as the MCE, becomes weak due to the enhanced saturated magnetization of martensites. We also studied the effect of Fe/Co co-doping in Ni45(Co1−xFex)5Mn36.6In13.4 metamagnetic alloys. Introduction of Fe atoms can assist the conversion of the Mn—Mn coupling from antiferromagnetic to ferromagnetic, thus maintaining the strong metamagnetic behavior and large MCE and MR. Furthermore, a small thermal hysteresis but significant magnetic hysteresis was observed around TM in Ni51Mn49−xInx metamagnetic systems, which must be related to different nucleation mechanisms of structural transition under different external perturbations.

Magnetocaloric effects in RTX intermetallic compounds (R = Gd–Tm, T = Fe–Cu and Pd, X = Al and Si)*

The ternary intermetallic RTX compounds (R = rare earth, T = transitional metal, X = p-block metal) have been investigated extensively in the past few decades due to their interesting physical properties. Recently, much attention has been paid to the magnetocaloric effect (MCE) of these RTX compounds, especially the ones with heavy rare-earth, for their potential application in low temperature magnetic refrigeration. In this paper, we review the MCE of RTSi and RTAl systems with R = Gd~Tm, T = Fe~Cu and Pd, which are widely investigated in recent years. It is found that these RTX compounds exhibit various crystal structures and magnetic properties, which then result in different MCE. Large MCE has been observed not only in the typical ferromagnetic materials but also in the antiferromagnetic materials. The magnetic properties have been studied in detail to discuss the physical mechanism of large MCE in RTX compounds. Particularly, some RTX compounds, such as ErFeSi, HoCuSi, HoCuAl, etc, exhibit large reversible MCE under low magnetic field change, which suggests that these compounds could be promising materials for magnetic refrigeration in low temperature range.The magnetocaloric effect (MCE) of RTSi and RT Al systems with R = Gd–Tm, T = Fe–Cu and Pd, which have been widely investigated in recent years, is reviewed. It is found that these RTX compounds exhibit various crystal structures and magnetic properties, which then result in different MCE. Large MCE has been observed not only in the typical ferromagnetic materials but also in the antiferromagnetic materials. The magnetic properties have been studied in detail to discuss the physical mechanism of large MCE in RTX compounds. Particularly, some RTX compounds such as ErFeSi, HoCuSi, HoCuAl exhibit large reversible MCE under low magnetic field change, which suggests that these compounds could be promising materials for magnetic refrigeration in a low temperature range.

Large magnetic entropy change and magnetic properties in La (Fe1-xMnx)11.7Si1.3Hy compounds

Magnetic properties and magnetic entropy change in La (Fe1-xMnx)11.7Si1.3Hy compounds have been investigated. A significant increase of the Curie temperature TC and a small increase of the saturation magnetizations µS have been observed after the introduction of interstitial H, which caused a slight volume expansion. The first-order field-induced itinerant-electron metamagnetic (IEM) transition remains and brings about a large magnetic entropy change around room temperatures for the compounds. The maximal magnetic entropy change is about 23.4, 17.7 and 15.9J/kgK under a magnetic field change from 0 to 5T for x=0.01, 0.02 and 0.03, respectively. Therefore, the compounds appear to be potential candidates for magnetic refrigerants around room temperatures.