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Structure and magnetic properties of Gd 4 Mn 0.05 Sb 0.95 3a Department of Physics, Chungbuk National University, Cheongju 361-763, South Korea b Center for Materials Science, National

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Structure and magnetic properties of Gd 4 (Mn 0.05 Sb 0.95 ) 3

a Department of Physics, Chungbuk National University, Cheongju 361-763, South Korea

b Center for Materials Science, National University of Hanoi, 334 Nguyen Trai, Hanoi, Viet Nam

Abstract

This work studies the structure and magnetic properties of Gd4(Mn0.05Sb0.95)3with the aim to clarify the role played

by the magnetic Mn atom.Upon substitution of Mn for Sb in the parent Gd4Sb3 compound, it is found that the inverted Th3P4-like structure has been somewhat expanded.The Curie temperature is increased while magnetic moment, measured in the field of 50 kOe at 200 K, is slightly reduced.The ferromagnetic semiconductor,

Gd4(Mn0.05Sb0.95)3, undergoes a ferromagnetic to paramagnetic transition at 270 K.Observed anomalies occur in the magnetization vs.temperature curves measured in a very low magnetic field.They are attributed to magnetic inhomogeneities resulting from a structural modification in Gd4(Mn0.05Sb0.95)3

r2002 Elsevier Science B.V All rights reserved

PACS: 75.50.Pp; 75.30.Cr

Keywords: Gd 4 (Mn 0.05 Sb 0.95 ) 3 ; Structure; Inhomogeneity; Magnetic phase transition

1 Introduction

Following the recent discovery of III–V-based

diluted magnetic semiconductors, which can be

prepared by molecular-beam epitaxy by

substitu-tion of Mn for Ga in GaAs, many interesting

phenomena that are combinations of electrical,

optical and magnetic properties are observed.Of

special interest is the possibility to incorporate

magnetic effects in semiconductors to develop

effects needed for devices applications [1–2].As

reported in Ref.[3], the Curie temperature of the

diluted magnetic semiconductor (Ga,Mn)N can be

tuned in the wide temperature range of 228–370 K

by varying the Mn content.It is noteworthy that,

in the ferromagnetic semiconductors (Ga,Mn)N

[3] and Ga0.98Mn0.02As [4], it cannot be shown which are the Mn atoms participating in the ferromagnetism and which are the paramagnetic

Mn atoms.This is thought to be attributed to magnetic inhomogeneity in the material, which is caused by the partial participation of Mn atoms in the ferromagnetic ordering[4].Thus, it is desirable

to further clarify the role of Mn in magnetic semiconductors

In the present work, the effects of Mn substitu-tion for Sb on the magnetic and structural properties of Gd4(Mn0.05Sb0.95)3were investigated

2 Experimental

Gd4(Mn0.05Sb0.95)3 was prepared by arc-melt-ing.The alloy was annealed at 11001C.The details

*Corresponding author.Tel : 43-261-2270; fax:

+82-43-274-7811.

E-mail address: skoh@chungbuk.ac.kr (S.K Oh).

0921-4526/03/$ - see front matter r 2002 Elsevier Science B.V All rights reserved.

PII: S 0 9 2 1 - 4 5 2 6 ( 0 2 ) 0 1 7 7 5 - 1

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of the sample preparation will be reported

else-where[5].Structural analyses were made based on

the extended X-ray absorption fine structure

(EXAFS) and X-ray diffraction.EXAFS

experi-ments were carried out at the 7C EC EXAFS beam

line of the Pohang Light Source (PLS) in Korea

The magnetization was measured in a Quantum

Design MPMS-5 SQUID magnetometer from 5 to

300 K in magnetic fields up to 50

kOe.Measure-ments of the real and imaginary parts of the AC

susceptibility were carried out from 70 to 300 K in

a Lakeshore 7000 Susceptometer

3 Results and discussions

Compared with the parent Gd4Sb3 compound

[7–9], we found that the inverted Th3P4-like

structure has been somewhat expanded and the

lattice constant of Gd4(Mn0.05Sb0.95)3 was

deter-mined to be 9.402 (A.For comparison, we have

summarized in Table 1 the lattice constants of

Gd4Sb3 and Gd4(Mn0.05Sb0.95)3 from several

different studies.One can see that partial

replace-ment of Sb by Mn in the parent Gd4Sb3compound

increases the volume of the unit cell.Similar

behavior was observed in Ga1xMnxAs [6] and

Gd4(SbxBi1x)3 [7] compounds.As reported in

Ref [7], in Gd4(SbxBi1x)3 compounds, as the

doping concentration x is increased, the lattice

constant a0 decreases from 9.38 (A for Gd4Bi3 to

the value 9.22 (A for Gd4Sb3.Additionally, a

decrease of the Curie temperature TC with

increasing Sb content has been reported [7].The

decrease of TC and a0 with increasing Sb content

in Gd4(SbxBi1x)3 may be due to the smaller

atomic radius of Sb compared to Bi.The larger

atomic radius of Mn in comparison with Sb is probably the origin of the increased lattice constant of Gd4(Mn0.05Sb0.95)3 with respect to the pure Gd4Sb3compound.In order to study the influence of Mn substitution in Gd4Sb3, we have studied the magnetic properties of both Gd4Sb3

and Gd4(Mn0.05Sb0.95)3.InFig.1, the temperature dependence of the magnetization of both com-pounds is shown, measured in an applied field of

100 Oe from 5 to 300 K.For both Gd4Sb3 and

Gd4(Mn0.05Sb0.95)3 samples, there is a prominent difference between the FC (field-cooled) and ZFC (zero-field-cooled) magnetization below TC; indi-cative of magnetic frustration arising from the competition between ferromagnetic and antiferro-magnetic interactions [10].Obviously, both

Gd4Sb3and Gd4(Mn0.05Sb0.95)3are ferromagnetic

in the whole temperature range below the Curie temperature.The TCvalues were determined to be

259 and 270 K for Gd4Sb3and Gd4(Mn0.05Sb0.95)3, respectively.Substitution of Mn for Sb in the parent Gd4Sb3 compound not only increases the volume of the unit cell but also increases the TC: This is consistent with the result reported earlier

by Holtzberg et al [7].The M vs T curve

Gd4(Mn0.05Sb0.95)3 exhibits slightly anomalous behavior in the temperature region from 150 to

255 K suggesting some kind of phase transition

To further clarify this situation, measurements of the real and imaginary parts of the AC suscept-ibility were performed.As can be seen in Fig.2, the real (w0) and imaginary (w00) parts of the AC susceptibility of the sample reveal similar unusual behavior.Since no anomalous behavior is found

in the temperature dependence of the parent compound Gd4Sb3, the small anomalies in the

M vs T curves of Gd4(Mn0.05Sb0.95)3 can safely

Table 1

Lattice constant a0; the magnetization M50 kOe; measured in 50 kOe at 200 K and the Curie temperature TC for Gd 4 Sb 3 and

Gd 4 (Mn 0.05 Sb 0.95 ) 3

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be attributed to the presence of Mn in this sample The presence of very small amount of about 0.14% Mn (confirmed by EXAFS analysis) causes

a structural modification in the sample, which in turn causes magnetic inhomogeneities.They may

be the origin of the anomalous behavior of the magnetization in the temperature region from 150

to 255 K, before the onset of ferromagnetic-paramagnetic phase transition.The value of magnetic moment of Gd4(Mn0.05Sb0.95)3, mea-sured in the field of 50 kOe at 200 K, is only slightly a bit smaller than that of Gd4Sb3(Fig.3), but the presence of Mn in Gd4Sb3 causes the material to exhibit much softer ferromagnetic behavior (Fig.1).A similar effect has been reported for Gd4(SbxBi1x)3 compounds by dop-ing with Bi[7]

0

1

2

3

4

5

6

T

C = 259 K

0

1

2

3

4

Gd4Sb3

T (K)

ZFC

FC

Gd

3

TC= 270 K

H = 100 Oe

ZFC

FC

T (K)

Fig.1 Temperature dependence of the magnetization at 100 Oe

for both zero-field-cooled (ZFC) and field-cooled (FC) Gd 4 Sb 3

(top panel) and Gd 4 (Mn 0.05 Sb 0.95 ) 3 (bottom panel).

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

50 100 150 200 250 300 0.000

0.004

0.008

0.012

0.016

T (K)

Gd4(Mn0.05Sb0.95)3

, (arb units)

Temperature (K)

HAC = 10 Oe

f = 80 Hz

Fig.2 Temperature dependence of the real (w 0 ) and imaginary

(w00) parts of the AC susceptibility of Gd (Mn Sb )

0 20 40 60 80 100

0 20 40 60 80 100

H (Oe)

Ga4(Mn0.05Sb0.95)3

T = 200 K

H (Oe)

Gd

3

T = 200 K

Fig.3 Magnetic-field dependence of the magnetization at

200 K for both Gd 4 Sb 3 (top panel) and Gd 4 (Mn 0.05 Sb 0.95 ) 3

(bottom panel).

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In order to further elucidate the nature of the

magnetic transition, magnetization vs.magnetic

field isotherms of Gd4(Mn0.05Sb0.95)3 were

mea-sured in the vicinity of TC: As can be seen inFig.4,

the M2H curves show a normal monotonic

decrease of the magnetization with increasing

temperature.This might be due to a monotonic

phase transition and a weak coupling between spin

and lattice in the magnetic ordering process arising

from inhomogeneity in the sample [11].Similar

behavior has also been observed for the parent

compound Gd4Sb3[7]

4 Conclusions

The structural and magnetic properties of

Gd4(Mn0.05Sb0.95)3 were investigated.The partial

replacement of Sb by Mn in the parent compound

Gd4Sb3causes an expansion of the inverted Th3P4

-like structure and an increase of the Curie

temperature of about 10 K.The presence of Mn

in Gd4Sb3 causes a small anomaly in the

ferro-magnetic behavior.The ferroferro-magnetic semicon-ductor, Gd4(Mn0.05Sb0.95)3 undergoes the ferromagnetic to paramagnetic transition at

270 K.The observed anomalies in the magnetiza-tion vs.temperature curves, measured in a very low magnetic field, are likely to be attributed to magnetic inhomogeneities resulting from a struc-tural modification in Gd4(Mn0.05Sb0.95)3

Acknowledgements This work was supported by the Korea Re-search Foundation Grant (KRF-2001-005-D20010)

References [1] A.Oiwa, S.Katsumoto, A.Endo, M.Hirasawa, Y.Iye, H Ohno, F.Matsukura, A.Shen, Y.Sugawara, Solid State Commun.103 (1997) 209.

[2] F.Matsukara, H.Ohno, A.Shen, Y.Sugawara, Phys.Rev.

B 57 (1998) R2037.

[3] M.L Reed, N.A El-Masry, H.H Stadelmaier, M.K Ritums, M.J Reed, C.A Parker, J.C Roberts, S.M Bedair, Appl.Phys.Lett.79 (2001) 3473.

[4] H Ohldag, V Sonilus, F.U Hillebrecht, J.B Goedkoop, M.Finazzi, F.Matsukura, H.Ohno, Appl.Phys.Lett.76 (2001) 2928.

[5] Nguyen Ngoc Chau, Manh-Huong Phan, to be published [6] S.J Potashnik, K.C Ku, S.H Chun, J.J Berry, N Samarth, P.Schiffer, Appl.Phys.Lett.79 (2001) 1495 [7] F Holtzberg, T.R McGuire, S Methfessel, J.C Suits, J.Appl.Phys.35 (1964) 1033.

[8] R.J Gambino, J Less-Common Metals 12 (1967) 344 [9] G.Borzone, M L.Fornasini, N.Parodi, R.Ferro, Intermetallics 8 (2000) 189.

[10] J.G Park, M.S Kim, H.C Ri, K.H Kim, T.W Noh, S.W Cheong, Phys.Rev.B 60 (1999) 14804.

[11] S.E Lofland, K.V Ramanujachary, W.H McCarroll, J.Magn.Magn.Mater.238 (2002) 22.

0

50

100

100 K

160 K

200 K

220 K

240 K

260 K

265 K

270 K

275 K

280 K

285 K

290 K

300 K

H (Oe)

Fig.4 Magnetization vs field for Gd 4 (Mn 0.05 Sb 0.95 ) 3 at

various temperatures in fields up to 50 kOe.The temperatures

of the isotherms are indicated.

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