Colossal Magnetoresistance of MexMn1-xS (Me = Fe, Cr) Sulfides

G. A. Petrakovskii et al., JETP Lett. 72, 70 (2000) Y. Morimoto et al., Nature 380, 141 (1996)

Shimizu-group HANZAWA Akinori

Contents
Introduction
Colossal Magnetoresistance (CMR) LaMnO3 MexMn1-xS (Me = Fe, Cr) Motivation

Experimental method
Results and Discussion

Summary

introduction

Colossal Magnetoresistance (CMR)

There are 2 types of CMR.
At hard disk, Fringing field () is very low, so disk head must be magnetic-field-sensitive.

1. On applied external magnetic field for sample, electrical resistance noticeably increase.

2. On applied external magnetic field for sample and doped hole, electrical resistance noticeably decrease and phase change from paramagnetic to ferromagnetic.

At this paper, they focus on this CMR.

introduction

LaMnO3
Manganese oxides with the cubic perovskite structure.
Crystal structure
Perovskite structure

electron state
3d4 (Mn3+) eg electrons are strongly hybridized with the oxygen 2p states, so eg electrons are conduction electron.

t2g electrons can be viewed as localized spins with S=3/2.

energy state of 3d electron of Mn3+

introduction

LaMnO3
LaMnO3 is Mott insulator.
Antiferromagnetic insulator
Mott InsulatorSpins are alternately up and down. When coulomb repulsion for two electrons in a Mn is large, Electrons cannot move freely.

Carriers are doped in eg orbital.

Electrical conduction is provided.

For example, La1-xSrxMnO3 doped cation

Substitute divalent(2) cation (Sr2+, Ca2+ etc.) for trivalent(3) cation (La3+)

Mn3+ and Mn4+ are present by doping cation.

introduction

La1-xSrxMnO3
Double-exchange interaction
Spins are paralleled in different orbital by Hunds rule.

(a) t2g electrons (localized spins) are paralleled :

eg electron can transfer to Mn4+, because energy is not changed if any eg electron is exist which site.

(b) t2g electrons (localized spins) are antiparalleled : eg electron cannot transfer to Mn4+, because to transfer results in a loss of energy of Hunds rule.

Paralleled t2g electrons work ferromagnetic interaction.

This is double-exchange interaction.

introduction

La1-xSrxMnO3
t2g spins are leant. The formula of transfer integral (t) is this.

External magnetic field aligns the t2g spins and reduces the carrier scattering by the local spins.

ferromagnetic phase is stabilized for high temperature.

A steep rise of the magnetization observed around 130 K. Tc : The critical ferromagnetic transition temperature
T dependence of resistivity for single crystal of (LaxSr1-x)3Mn2O7. The resistivity with the current parallel (rab) and perpendicular (rc).

introduction

MexMn1-xS (Me = Fe, Cr)

Manganese sulfides with the rock salt structure.
Crystal structure
Rock salt structure
(NaCl structure)

Mn
Mn2+ ions are in the octahedral position s of the sulfur cubic lattice.

MnS (not doping) is Mott insulator.

The features of MexMn1-xS O S : It increases electron orbital overlap. NaCl structure : Rock salt structure is core of Perovskite structure.

introduction

Motivation
To observe Colossal magnetoresistance of non-perovskite MexMn1-xS (Me = Fe, Cr) To observe magnetic order of MexMn1-xS (Me = Fe, Cr)

Experimental method
sample : MexMn1-xS (Me = Fe, Cr) polycrystal
x of Fe is 0.29. x of Cr is 0.5

measurement
X-ray structural analysis : monochromatic Cu Ka radiation
Temperature range 100~300 K

Electrical resistance measurement : Temperature range 4.2~300 K

Magnetic field H = 0, 2, 10, 30, and 50 kOe

Magnetic properties : measured on vibrating-coil magnetometer with

superconducting solenoid at 30 kOe Temperature range 77~300 K
10 kOe = 1 T

Result

Fe0.29Mn0.71S

According to X-ray data, the Fe0.29Mn0.71S undergoes a structural transition at Ts ~ 147 K.

Similar transition is observed in MnS. Rhombohedral distortion

The lattice parameter is independent of temperature at 120~140 K.

Lattice distortion is occurred.

The conduction in the samples is of the semiconductor type with thermal hysteresis.

Temperature-dependent (a) lattice parameter, (b) magnetization, and (c) resistivity of Fe0.29Mn0.71S

Result

Fe0.29Mn0.71S

At 30 kOe, the negative magnetoresistance dH reaches -450 % at ~50 K.

At 50 kOe, this value is -87 %.

Temperature curves for the magnetoresistance dH of Fe0.29Mn0.71S at 10, 30, and 50 kOe.

Its found that FexMn1-xS have a colossal magnetoresistance .

Result

Cr0.5Mn0.5S
This sulfide undergoes the antiferromagnetferromagnet transition at 66K.
The nature is caused by JahnTeller effect.

At 30 kOe, the negative magnetoresistance dH reaches -25 % at ~4.2 K.

The transition to the negative magnetoresistance occurs in the range of magnetic transition.
Temperature curves for the magnetization (a) and magnetoresistance (b) of Cr0.5Mn0.5S at 30 kOe.

Its same behavior of La1-xSrxMnO3

Its found that CrxMn1-xS have a colossal magnetoresistance .

Discussion
Electrical and magnetic properties of MexMn1-xS are similar to those observed for La1-xSrxMnO3.
analogous point the cubic lattice is distorted in the range of appeared CMR. LaMnO3 and MnS (not doping) are Mott insulator. AF semiconductor-FM metal are produced in cation-substituted LaMnO3 ( or MnS).
The regions of antiferromagnetic semiconductor and ferromagnetic metal coexist. (by Mssbauer data)
G.V. Loseva et al., Phys, Solid States 25, 2142 (1983)

But, the mechanism of CMR effect still remains to be clarified.

Summary
Colossal magnetoresistance is observed in non-perovskite MexMn1-xS (Me = Fe, Cr). This MexMn1-xS sample has little data. So, this sample must be given results and should be understood the magnetism mechanisms.

My study

MexMn1-xS

The less interspace of octahedral structure, the more increase electron transfer. MexMn1-xS (Me = Fe, Cr) may appear metallic state. One way is ion substitution.

Other way ?

apply hydrostatic pressure

For FexMn1-xS, x = 0.29 is critical concentration of metal transition.
FexMn1-xS which its concentration is no more than x = 0.29 apply hydrostatic pressure, the sample appear metallic state.

I anticipate that CMR will be observed in MexMn1-xS (Me = Fe, Cr) by pressure.