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 1

CHALCOGENIDES AND PNICTIDES

PART B: MAGNETIC TRANSITION METAL PNICTIDES

Daniel FRUCHART

Laboratoire de Cristallographie, CNRS, BP 166

38042 Grenoble Cedex 9 France

In book: Handbook on Magnetism and Advanced Magnetic Materials - Novel Materials,

Edition: HMM, Chapter: Chalcogenides and Pnictides, Publisher: J. Wiley and Sons, Editors:
H. Krönmuller, S. Parkin, (2007) pp.2378-2400
keywords

Transition metal magnetism

Pnictides

Magnetocaloric materials
 2

I. INTRODUCTION

Transition metal-rich phosphides and arsenides or antimonides (X = P, As, Sb) exhibit

very peculiar but strongly related crystal structures leading to fairly marked magnetic

characteristics. Both the magnetic ordering temperatures and the local magnetic moments of

transition elements (T) usually range not so far to those of the metals and alloys, respectively.

In fact, the main series of TT’X and TX metal type compounds display nearest metal-metal

distances 10 to 20% larger only than in pure metal compounds [Fruchart, R. 1982]. Contrarily

to halides, oxides and chalcogenides, here the size of the non-metal element X is effectively

smaller, the ionic-covalent character of the T-X bonds is less marked profit made to the

metallic characteristics of phosphides and arsenides. This peculiarity stands as well for the

classes of closely structured TT’X and TX compounds where X = Si, Ge, Sn, Sb….. e.g. with

MnAlGe on one side and MnSb on the other.

Besides it exists ternary pnictides series, e.g. skutterudites phosphides or antimonides

[Leithe-Jasper et al., 2004], or more complex systems e.g. Zr2Fe32P8 [Le Sénéchal C. et al.,

1999] of generic formula □n(n+1)Rn(n-1)T6(n2+1)X2(2n2+1)+1 (where R is a rare earth element, □ is a

vacancy) that most of time exhibit either magnetic properties at low temperature only, or are

weakly polarized with small moment if any. They will not be discussed here since they

exhibit weak magnetic characteristics, often disperse and moreover peculiar magnetic

components and couplings. Also the binary and ternary transition metal nitrides will not be

considered here since the marked interstitial character of X = N in many metal lattices, leads

to better compared to those of parent metal carbides, even borides. The coordination

polyhedron of nitrogen in transition metal nitrides is quite different than in compounds with a

less metallic type such as phosphides, arsenides, antimonides.

 3

Nevertheless, the magnetic properties of the two main series TX and TT’X here

considered remain dominated by direct metal-metal interactions [Fruchart, R., 1982], however

the T-X bonds leads to a reduction of the magnetic polarization reference to the orbital

scheme of pure a ionic state and supports marked competition of exchange forces.

Additionally for several compounds, rather strong magnetic moments (larger than ~ 3 µB for

Mn) have been measured. In fact, the classes of TX and TT’X materials are also characterized

by instabilities of the local magnetic polarization, with a possible impact on long range

magnetic ordering and in most cases are accompanied by structural transitions.

Early, J.B. Goodenough has focused his interest on those two series of peculiar

compounds thus establishing conceptual phase diagrams [Goodenough, J.B., 1972,

Goodenough, J.B., 1976] and proposed a general analysis of the subtle physical and magnetic

aspects of T metal pnictides in terms of electron filling orbitals, regard to characteristics

intermediate between metal and ionic types.

Such singular behaviors let to renew a marked interest to both series of TT’X and TX

metal phosphides and arsenides since high performance magnetocaloric properties have being

revealed quite recently. Promisingly, their corresponding magnetic transitions spread in a

wide range of temperature for large changes of magnetization, moreover being induced by

moderate magnetic fields as delivered by modern permanent magnet, e.g. NdFeB type.

II. CRYSTAL STRUCTURE RELATIONSHIPS

The TT’X series of compounds exhibit peculiar structural arrangements as a

consequence of sensitive T-T’ metal interactions. From a unique pseudo unit cell (block)

containing one formula unit (f.u.) the very rich series of polytype structures labelled T2

(Tetragonal, 2 f.u./cell), H3 (Hexagonal, 3 f.u./cell), O4 (Orthorhombic, 4 f.u./cell), O8,

 4

H12… are derived [Artigas, M., 1990]. The elementary block is defined as a pseudo-rhombic

unit cell, where the X atoms form two types of interstices, two with tetrahedral coordination,

T, and two of five-fold coordination with the shape of square-based pyramids, P. The three

fundamental polytype members crystallise either with the Cu2Sb (SG: P4/nmm), the Fe2P

(SG: P 6 2m) or the Co2P (SG: Pnma) type structure. These structures are strongly related

since the different point symmetry groups allow one to built compact but different

arrangements of blocks with respect to the fourfold, threefold and twofold symmetries,

respectively. The three main TT’X structures are represented in Figure 1, as well as the

rhombic pseudo unit cell containing one formula unit that is defined from a triangular channel

formed by the X atoms.

Analogies can be established between the different crystal structures of the former

series and those of the T’X one. Here, one of the metal atom (T’) is “missing”, the

corresponding tetrahedron, T, being empty, thus the T metal atom occupies the centre of the

octahedron formed from two neighbouring pyramids, P. The corresponding crystal structures

are the NiAs hexagonal type (H2, SG: P-3/mmc) and the MnP orthorhombic type (O4, SG:

Pnma) as seen on Figure 2. Both the TX crystal structures are directly related since the

second one can be considered as the ortho-hexagonal distorted variant, the T atom being

shifted from the centre of the octahedron as a bi-pyramid, alternately in one or other of the

two pyramids.. In fact, the series of TX and TT’X pnictides derive from the NiAs, or its filled

form Ni2In via displacive or distortive types of transformations.

For both series TT’X and TX more dense structures (short and short metal – metal

distances) are obtained by application of external pressure or chemical pressure [Krumbugel-

Nylund, A., 1974a] following the succession T2 (TT’X) to H3 (TT’X and TX) to O4 (TT’X

and TX). The magnetic coupling forces being intimately related to the metal to metal

distances directly depending on the crystal structure taken by the TT’X or TX compounds,
 5

consequently magneto-elastic transitions take place systematically with changes of both the

crystal and magnetic structures (e.g. ferro to AF in the MnAs – FeAs system [Krumbugel-

Nylund, A., 1974b]). The competing magnetic interactions promote the presence of

metastable non-collinear, long range ordering arrangement, leading to metamagnetic

behaviours versus the applied magnetic field. As well, instabilities of electronic origin are

common to observe, and abrupt changes of the metal atom magnetization level can

accompany the structure transition that are often of first order type;

III. GENERAL OVERVIEW ON MAGNETIC PROPERTIES

The structural and magnetic characteristics of most intermetallic compounds of

transition elements, namely the pnictides formed with P, As and Sb, have been extensively

reviewed fifteen years ago by Beckmann and Lundgren [Beckmann, O., and Lundgren, L.,

1991]. One is invited to report to this excellent review in what may concern most the

compounds already studied before. As above mentioned, one can easily recall the most

pertinent phase diagrams, as reported vs composition, stoichiometry or external pressure, thus

well illustrating dramatic interplays between crystal structures and opposite magnetic

couplings.

Both the series of pnictides here discussed reveal optimal magnetic properties

corresponding well to a peculiar valence electron concentration (VEC) and leads to extreme

ordering temperatures or (and) large magnetization levels. Whatever is the crystal structure of

the considered TT’X polytypes, the maximum TC of most compounds takes place close to the

d6 configuration (Fe), as for Fe2P, MnCoP, MnCoAs, CrNiAs… [Fruchart, R. 1982]. This

applies as well to the solid solutions and multinaries. E.g., Figure 3 presents the huge

variation of both Curie temperature in the Mn1-xCoxP system and magnetization, as reported
 6

earlier [Fruchart, D. et al. 1980]. For the optimized VEC value, ferromagnetic couplings are

most of time dominating, but upon a slight change of composition or application of pressure

(chemical or external pressure) dramatic situations take place with abrupt drops of

magnetization. Then, AF couplings control the long range magnetic ordering which is often

incommensurate with the crystal cell. The situation is perfectly illustrated in Figure 4a to

Figure 4c, all related to Fe2P. In the vicinity of the change of ordering, both the ferro-

antiferromagnetic and ferro-paramagnetic transitions are accompanied with either a change of

crystal structure, or at least with discontinuities of the cell parameters. Simultaneously, the

magnetic moment of the T (T’) element can vary abruptly as the electronic state becomes

modified [Bacmann, M. et al. 1994]. Additionally in the paramagnetic state, short range

magnetic ordering effects have been observed with a regime of high temperature correlation

up to 3 TC [Zach, R., et al. 1994; Zach, R., et al. 1995-a; Zach, R., et al. 1995-b].

Very similar instability effects, also of electronic origin, have been pointed out in the

TX series, as illustrated in Figure 5 for the CrP – MnP – FeP system [Sénateur, J-P. et al.

1969; Beckmann, O., and Lundgren, L., 1991]. The well known lattice and magnetic

instability of MnAs [Goodenough, J.B. and Kafalas, J.A. 1967] versus temperature,

composition and application of pressure are more particularly illustrated by the dual Figure

6a vs composition and Figure 6b vs application of an external pressure.

More recent fundamental investigations on the properties of the TT’X series have been

reported all along the 90’s up to now, mostly by T. Kanomata et al in Japan, R. Zach et al in

Poland, D. Fruchart et al in France, J. Bartolomé et al in Spain, for a part under crossed

collaborations, and by E. Brück et al in The Netherlands. After the discovery of the very

important MCE in MnAs by H. Wada et al in Japan, S. Gama et al in Brazil have evidenced

colossal MCE properties of MnAs1-xSbx systems under pressure.

These contributions can be classified relative to their main objectives and interests, as:
 7

1 – investigation of the magnetic and electronic structures,

2 – correlation of the typical magnetoelastic behaviors with the crystal and magnetic

transformations at specific transitions,

3 - transformations induced applying external pressure or high magnetic fields,

4 – specific analysis of the change of entropy at transition in terms of magnetocaloric

effect.

III.1 Investigation of the magnetic and electronic structures

III.1.1 TT’X pnictides

Fe2P remains a material of reference because of the multiple magnetic and physical

sensitive characteristics obtained with the pure and substituted compounds. Band structure

calculations using a KKR-CPA method were performed to compare with the experimental

results gained by a combination of magnetization and neutron diffraction measurements on

Fe2P [Koumina A. et al. 1998] and on FeMnP1-xAsx compounds [Tobola J. et al. 1996]. A

fairly good agreement was realized in determining the magnetic moments from experience

and calculations. The re-entrant spin-glass (SP) type transition at T ~ 125 K of Fe2P

substituted by small amounts (5%) of both Cr and Ni was studied by DC magnetization and

AC susceptibility [Srivastava, B.K. et al. 1994]. The critical exponent of the freezing

phenomenon was determined, thus ranging well with values observed for ordinary

paramagnetic SP transitions. The magnetic phase diagram of slightly Cr-substituted Fe2P

samples was determined from magnetization and neutron diffraction experiments. Three

different regions were identified reference to an intermediate range (50 < T < 120 K) where

negative interaction forces reveal important comparison made with low and high ranges of
 8

temperatures respectively, both exhibiting ferromagnetic type orderings [Sudish-Kumar, et al.

1999].

The dependence of the thermopower Seebeck coefficient S(T) [Nakama, T. et al 1998]

was measured versus polarization of the magnetic structure by application high magnetic

fields up to 15 T. A large field dependence was found with a shoulder between 60 and 70 K

and a discontinuity at “TC”, a first order type transition.

The magnetic phase diagram of MnRhAs (H3 type) was re-analyzed using single

crystal and a.c. susceptibility technique in order to better precise the metastable character of a

so-called ferro-AF multi-step transition taking place between 127 and 176 K. Three zones

with different behaviors have been evidenced to relate to spin canting phenomena [Rillo, C. et

al. 1992].

The ferromagnetic (Fe1-xRux)2P (H3 type) system was investigated using the same

technique as above, thus revealing two magnetic transitions, the role of increasing Ru content

being interpreted similar to the application of high pressure on the binary Fe2P [Artigas, M. et

al. 1992], the later being re-analyzed by neutron diffraction and band structure calculations

[Tobola, J. et al. 1996]. A comparison was established with the parent MnFeP0.7As0.3 where a

drop of magnetic moment of Fe was evidenced earlier at ferro-AF transition.

Following the phase diagram re-investigation [Bacmann, M. et al. 1990] of the (Mn1-

xFex)2P (H3 type) by A.C. susceptibility, new magnetic phases were detected, in agreement

with a parallel neutron diffraction analysis. The system (Mn1-xCox)2P (O4 type) isoelectronic

to Fe2P (H3 type) for x = 0.5 was analyzed parallel by magnetization measurements and band

structure calculation [Sredniawa, C. et al. 2002]. In agreement with the magnetic

arrangements as determined elsewhere by neutron diffraction, the rapid drop of phase

transitions induced by higher and higher Mn contents was correlated with a marked

enhancement of density of states (DOS) close to the Fermi level. Complementary to the two
 9

above ternary systems, analysis of the pseudo quaternary MnFe1-xCoxP system by different

experimental techniques and band structure calculations [Sredniawa, C. et al. 2001] reveal a

very interesting phase diagram with a first order AF-ferro transition sensitive to composition.

This orthorhombic phase diagram appears quite similar to the hexagonal part of the MnFeP –

MnFeAs hexagonal system [Bacmann, M. et al. 1994, Tobola, J. et al. 1996,]. Substitution of

Si to P in MnFeP was shown possible up to x ~ 0.4, however the thermal treatment history

dependence reveal unexpected and puzzling effects in terms of Curie temperature [Zhang, L.

et al. 2005].

Magnetization curves measured in a H3 (MnRuP) and in T2 (MnZnSb and MnGaGe)

systems around Curie temperature to determine the critical exponents [Ono, F. et al. 2001]

lead to the conclusion that the two dimensional magnetic character applies well for the later

T2 type-compounds, contrarily to the H3 one MnRuP. Systematic computational KKR-CPA

analyses of tetragonal arsenides, binary and ternary antiferromagnets (Cr2As, CrMnAs,

Mn2As, CrNiAs) were performed [Tobola, J. et al. 1997], revealing an excellent agreement

with the previous magnetic structure determination, namely using neutron diffraction.

However for the hexagonal CrNiAs compound, isoelectronic to Fe2P, reveals strong

competition between AF and ferromagnetic couplings, and it was anticipated that pressure

effects or substitution should increase the magnetic moment of Cr up to more than 2 µB. The

pressure effects have been studied in detail by S. Ohta et al as reported in part III.3. This

group report parallel on high fields magnetization performed on (Cr1-xNix)2As with x = 0.5,

0.7, concluding that the low temperature anomalous magnetization was to attribute to spin

glass like behavior related to band magnetism [Ohta, S. et al. 1995a]. From a band structure

analysis they concluded that CrTX systems with T = Fe, Co, Ni, X = P, As, Cr are

magnetically ordered but Cr carries a magnetic moment, only [Ishida, S. et al. 1996]. Finally,

a study based neutron diffraction [Bacmann, M. et al., 2004] revealed the low temperature
 10

phase of CrNiAs (up to ~ 110 K) consist in a sine modulated structure with moments on both

Cr and Ni, but up to TC ~ 210 K, only Cr carries a moment forming a simple collinear

structure.

More recently all possible magnetic exchange couplings that could take place in the

tetragonal series of TT’X pnictides were reviewed from theoretical symmetry approaches

[Fruchart, D., 2005]. Contrarily to most magnetic arrangements established up to now that

form AF collinear magnetic structures, long range non-collinear structures are basically

allowed in complete agreement with a first experimental result [Yamagishi, M. et al. 2000].

Here also, potential magneto-elastic couplings must be accounted to fully understand the

magnetic phase diagram as anticipated earlier [Shirakawa, H. et al. 1976].

Definitively, a systematic analysis of the magnetic couplings versus the metal-metal

distances in some TT’X with T = Cr and Mn, T = 4d elements (Ru, Rh, Pd) phosphides and

arsenides, leads to conclude that the physical behaviour should be interpreted as well in terms

of itinerant–electron magnetism [Ohta, S. et al 90, Kanomata, T. et al.1991] as revealed by

fitting the susceptibility traces

III.1.1. TX pnictides

For TX pnictides similar fundamental analysis were performed in order to better

understand the subtle equilibrium state between ferromagnetic and AF phase regions.

Symmetric and antisymmetric anisotropic exchange energies were considered for the relative

stability of the different modulated magnetic phase existing in the mono-pnictides MnP, FeP,

CrAs, MnAs [Sjöstrøm, J., 1992]. The results based on a band model analysis confirm that the

shape of the Fermi surface and the antisymmetric interactions are crucial for the stability of

the helical magnetic structure, e.g. in MnP.

 11

The magnetic couplings supported by conduction carriers were demonstrated of

relative importance to correlate the transport properties and magnetic ones [Barner, K. 1987].

As well, to mixed couplings was attributed the canted and helicoidal equilibrium spin

structure, with peculiar field and temperature dependence in MnPxAs1-x and CrxMn1-xSb

systems [Kohnke, H.J. et al. 1996].

MnP (O4 type) being one of the few magnetic systems in which an uniaxial Lifshitz

point (LP) has been identified, occurring at the confluence of a modulated, ferromagnetic and

paramagnetic phases. Experiments were performed applying the magnetic field along the

main direction of the orthorhombic cell, thus allowing to evaluate the critical exponent

parameters, e.g. susceptibility and specific heat [Beccera, C.C. et al. 2000]. The results have

been successfully interpreted in terms of a 3-D Ising model. Besides, from the analysis of the

wave vector dependence q(H) with the applied field of all the modulated magnetic structures

(helix, fan, cone) the shape of the magnetization curves realized applying the field along the

lattice vectors was explained as well as the nature of the cone-phase type transition [Zieba, A.

et al. 2000]. The characteristics of the Lifshitz point, triple point, critical end point, were

derived on the basis of an axial next nearest neighbor Heisenberg model (ANNNH), thus

appearing in semi-quantitative agreement with the experiments. Effective values for the cross-

over exponent, wave vector exponent and magnetization discontinuity provide explanations of

the deviation to experience. Apart from the mechanisms of phase transformation, the nature of

the O4 – MnP type magnetic structure was re-questioned theoretically by density functional

determination [Niranjan, M.K. et al. 2004]. The high temperature magnetic state was shown

to be antiferromagnetic and the absence of any Curie-Weiss type magnetic susceptibility was

justified by the lack of long-range ordering, according to the model.

III.2. Typical magnetoelastic behaviors

 12

A peculiar system MnFeP1-xAsx revealed soon very interesting since it contains the

three main structure polytypes O4 for the P rich side, T2 for the As rich side, H3 for

intermediate compositions as shown on Figure 7. Analysis of the dependence of magnetic

couplings vs the metal-metal distances (“densification” effect from T2 to H3 to O4), the

intermediate H3 part of the phase diagram reveals the existence of a singular transition TT at x

~ 0.27 between a ferromagnetic domain and an antiferromagnetic one. The so-called Curie

temperature “TC” from ferro to “paramagnetic” P state appeared having similar trends, first

order transition type with a magneto-elastic character, as the F – AF transition. The influence

of high magnetic fields was measured in the range 0 to 20 T from 4 to 400 K, thus inducing

magnetic phase transformations with magneto-elastic characters [Zach, R. et al. 1990]. Then

the magnetic ordering was checked for using several complementary techniques such as X-ray

and neutron diffraction vs temperature, Mössbauer spectroscopy and magnetic measurements

[Bacmann M. et al 1994, Zach R. et al 1995-a]. The a cell parameter drops down by ~ 1% at

the F – AF and F – P transitions TT and “TC”, conversely the c cell parameter increases by ~

2.5 %, thus almost no change of volume is observed. Crystal structure refinements indicate

that starting from the ferromagnetic state, the magneto-elastic transitions TT and “TC” led the

mean <Mn-Mn> (pyramidal sites) distance unchanged, the <Fe-Fe> (tetrahedral sites)

distance drops by 0.1 Å, conversely to the <Mn-Fe> which increase by the same value. A

high field X-ray diffraction investigation performed on MnFeP0.5As0.5 confirms the same

change of the a and c cell parameters when applying high field just above “TC”, however the

cell volume slightly and continuously decreases with increasing magnetic field through the

transformation [Koyama, K. et al. 2005], thus realizing the reverse behavior of the volume

expansion when temperature increases. Solving the complex non collinear and
57
incommensurate AF structure using both neutron diffraction and Fe Mössbauer
 13

spectroscopy indicate that at TT (and accordingly at “TC”) the magnetic moment drops down

by ~ 50% (0.6 µB), the magnetic moment of Mn being unaffected, close to 3 µB. All these

trends were confirmed later by KKR-CPA electronic structure calculations. Confirming most

of the characteristics of the MnFeP1-xAsx magnetic system was achieved more recently using
57
also Fe Mössbauer spectroscopy, but applied to close compositions as those previously

analyzed [Hermann, R.P. et al. 2004].

Both competing positive and negative interactions and a reduction of the Fe–M

exchange forces induce a ferromagnetic-paramagnetic magneto-elastic transition with a

marked loss of long range correlation just above “TC” as indicated by the important diffuse

scattering at large q vectors [Bacmann, M. et al, 1994]. A magneto-resistance study was

realized on MnFeP0.55As0.45 on a polycrystalline sample prepared by solid state reaction

[Tegus, O. et al, 2002a]. The extremum of the derivative of (T) coincides well with “TC”.

The increase of resistivity, which is almost constant in the RT range, approaching the

magnetic ordering temperature may be related to the existence of AF spin fluctuations. This

appears in agreement with what was proposed by R. Zach [Zach, R. et al 1995-a].

The critical field behavior was investigated experimentally [Zach, R. et al. 1995-b]

allowing to propose a Landau type of thermodynamic model as seen in Figure 8a to Figure

8c. This model was shown to be supported as well by systematic magnetic measurements

under pressure allowing to build a (T, B, P) diagram. [Zach, R. 1997].

Recently, a model description of the first order phase transition in MnFeP1-xAsx was

proposed [Tegus, O. et al. 2005b] based on the Bean-Rodbell model. Exchange interactions,

elastic energy, entropy and pressure terms and finally the Zeeman energy were used to

minimize the Gibbs free energy with respect to the volume and magnetization. The fit of

pertinent parameters to experimental data confirms that the magnetoelastic couplings play a

very important role in the mechanism of the phase transition.

 14

Besides, the magneto-elastic properties and electronic structure analysis for a similar

H3 system (Fe1-xNix)2P were determined recently [Zach, R. et al. 2004]. Once more, the

tetrahedral site where preferentially Ni substitutes for Fe losses rapidly its magnetic

polarization.

For both cases as for other ones of the TT’X series, the magneto-elastic character of

the first order type transitions is directly related to magnetic instabilities of electronic origin,

induced by chemical pressure effects.

III.3. Transformations induced by external pressure or high magnetic fields

Since the TT’X (and TX) systems of magnetic transition metal pnictides reveal very

dramatic competitions of coupling forces, with correlated magneto-elastic phenomena,

external pressure technique was used as well as high magnetic field to better understand the

nature of the transitions.

The MnRhAs (H3 type) compound revealed first very attractive regards to the

successive complex non collinear structure, AF at low temperature, transforming to a F + AF

state via a first order transition at TT = 158 K, then loosing long range ordering at TC ~ 200 K

[Chenevier, B. et al. 1984, Bacmann, M. et al. 1986]. Moreover antiphase magnetic

arrangements occur immediately down to TT as specially confirmed later by neutron

diffraction and topography [Chenevier, B. et al. 1992]. The pressure dependence of the

different transition was first investigated by Kanomata et al [Kanomata, H. et al. 1987]

indicating the stabilization of the AF domain at the expense of the F + AF one. This was

confirmed with more detail with the (T, B, P) phase diagram determined on the extended

MnRhAs1-xPx system [Zach, R. et al. 1992; Zach, R. et al. 1995; Zach, R. 1997]. Critical field
 15

exponent as well as triple point and end point were evidenced and interpreted using a Landau

type thermodynamic model as for the MnFeP1-xAsx system [Zach, R. 1997].

Pressure induced structural transition in the ferromagnet MnRhP (H3 type) and

MnRhAs at room temperature by using in-situ experiment [Eto, T. et al. 2000]. A

transformation to an orthorhombic (more dense) structure occurs under 34 GPa. Another but

unidentified transformation occurs as well for MnRhAs under 25 GPa. The Curie temperature

dependence of the former and ferromagnetic compound was checked under pressure,

revealing a c-plane dependence of the exchange forces [Nishino, M. et al. 2000]. The

magnetic characteristics of the second compound as submitted to external pressure, but in a

weaker pressure range than for the X-ray investigation, were determined by Fujii et al [Fujii,

N. et al 2001]. This experiment has allowed to establish a singular behavior as reported in

Figure 9, but in good agreement with earlier studies [Zach, R. et al. 1997]. For a pressure

larger than 5 GPa, an almost ferromagnetic phase was stabilized. Similarly a ferromagnetic

state was stabilized under pressure up to 12 GPa in the MnRhAs0.5P0.5 as a part of re-analysis

of the MnRhAs1-xPx.system with x = 0.4, 0.5 0.6 [Zach, R. et al. 1992; Fujii, N. et al. 2002a].

Finally, the related but more complex system MnRh1-xCoxAs .was investigated up to 8 GPa

for magnetic properties and using in situ experiments for X-ray analysis [Fujii, N., et al.

2002b]. MnCoAs (O4 type) is a ferromagnet and from substitution of Rh to Co, a reinforced

ferromagnetic state can be expected at the expense of the low temperature AF state. A

comparison of the results in terms of magnetic couplings acting along the c-axis, with those

recorded on parent compounds (MnRhP, MnRuP, MnRhAs, MnRhAs1-xPx., MnZnSb) allowed

the authors conclude that RKKY type interactions play an important role for the exchange

mechanism in TT’X system, as illustrated in Figure 10.

Other sensitive TT’X systems were investigated under pressure. With CrNiAs and

CrRhAs (both H3 type) for a similar phenomenology anticipated with both the CoxMn1-xP and
 16

MnRhAs1-xPx., systems. A decrease of the ordering temperature TC and TN respectively was

induced by application of pressure [Ohta, S. et al. 1995b; Ohta, S. et al. 1998].

Interestingly MnFeAs (T2 type) transforms and is stabilised to MnFeAs (H3 type) by

using high pressure (6 GPa) at temperature of 800°C. X-ray analysis of the cell parameters,
57
neutron diffraction to analyze both the crystal and magnetic structures, Fe Mössbauer

spectroscopy studies and KKR-CPA electronic structure calculations were undertaken

[Tobola, J. et al. 2001]. All results are in fair agreement with the fact that the Mn magnetic

moment (pyramidal site) is weakly reduced from T2 to H3 type, but for Fe (tetrahedral site), it

is almost zero for T2 is comprised between 1.1 to 1.54 µB, respectively, deduced from the

calculations and the experiments. This supports well the specific instable character of the

magnetic moment of Fe sitting in the tetrahedral site of the TT’X compounds as for

MnRhAs1-xPx.in the H3 range of compositions. Figure 11 represents the position of the Mn

and Fe magnetic moment vs the mean metal-metal distance.

Niziol et al have more particularly studied the (Co1-xMnx)2P system (x = 0.6 and 0.75),

namely using a.c. susceptibility measurement under external pressure [Niziol, S. et al. 1993].

The metastable character of the ferromagnetic state reference to the low temperature

incommensurate AF structure was correlated with a magnetovolume effect. The results led to

propose a localized/delocalized picture of magnetism.

In the past, the tetragonal compound Mn2Sb (T2 type) has retained long attention for

its ferrimagnetic characteristics up to relatively high temperature as reported in [Beckmann,

O., and Lundgren, L., 1991]. Under external pressure and using neutron diffraction, the ferri-

antiferromagnetic transition initiated when applying pressure for many of the parent

substituted compounds was not evidenced in pure Mn2Sb [Ryzhkovskii, V.M. et al. 2002].

Under a pressure of 2.8 GPa the pure binary antimonide is only characterized by a spin

reorientation phenomenon. Besides, it was shown earlier on a parent system [Val’kov, V.I. et
 17

al 1997] than cycles of thermal treatments applied on substituted Fe0.5Mn1.1As (T2 type)

allowed to suppress the low temperature phase down to 77 K, the material being still

ferromagnetic, contrarily to sample prepared in a conventional way.

In terms of field induced structural and magnetic transformations the monopnictide

series provides a very interesting result with MnAs [Ishikawa, F. et al. 2003; Ishikawa, F. et

al. 2004]. From both magnetization measurements and X-ray diffraction performed under

magnetic field a metamagnetic transition between paramagnetic to ferromagnetic state was

induced above TC. From the X-ray profile analysis, the forced magnetic state was stabilized

at ~ 3.5 T, and the first order crystalline and magnetic transition was deduced from a

particularly squared hysteresis loop, as reported in Figure 12.

IV. MAGNETOCALORIC PROPERTIES OF THE TT’X AND TX SERIES

VI.1. Thermodynamics of magnetocaloric materials

In order to understand the physical origin of the magnetocaloric effect, it is useful to

recall briefly the thermodynamic properties of a magnetic material plunged in a magnetic field

B. under constant pressure, the full entropy is given by:

S (T,B) = Slat (T) + Se (T) + Sm (T,B) (1)

which Slat, Se, Sm represent respectively the lattice entropy, the electronic entropy and

magnetic entropy. The magnetocaloric effect can be related to the magnetic properties of the

material through the thermodynamic Maxwell’s equation

 S   M 
    (2)
 B  T  T  B
 18

According to the magnetization measurements vs temperature and applied magnetic

field, the magnetic entropy change of a material can be calculated using this relation as

 M 
B
Sm (T ,0  B)     dB
'
(3)
0
T  B '

Considering the temperature variation M (T ) and equation (3), it is concluded that a

homogeneous magnetic material having a definite magnetic phase transition temperature, is

M
not suitable for use as the refrigerant, because varies considerably with temperature
T

change near TC and, as a result, entropy change takes the maximum accordingly, only.

Using magnetisation measurement made at discrete temperature intervals and by

numerical integration of equation (3), S m can be approximated as

M i 1  M i
S m   Bi (4)
i Ti 1  Ti

where M i 1 and M i are the magnetization values measured in a field B , at temperature Ti 1

and Ti respectively.

In the classical mean field theory the relative magnetisation is given by

2 j 1  2 j 1  1  1 
  B j ( y)  coth y   coth y  (5)
2j  2j  2j 2j 

where B j is the Brillouin function, j the total angular momentum. The argument y is the

solution to the simultaneous equations

  B j (y)

1   j  g j 
y 3TC    B B (6)
T   j  1)  k 

where k is the Boltzmann constant, g the Landé factor and  B the Bohr magneton.

According to principles of magnetism, the magnetic entropy is derived from:

 19

  2 j 1  
  sinh( 2 j y )  
Sm  R.ln    yB ( y ) (7)
  sinh( y )  
j

   
  2 j  

where R is the universal gas constant, and The changes of magnetic entropy caused by a

variation of magnetic field B  B f  Bi is given by:

S m (T , B  B f  Bi )  S m (T , B f )  S m (T , Bi ) (8)

Fore more deeper analyses, one can refer e.g. to the analytical model developed by P.J.

Ranke et al [von Ranke, P.J., et al. 2005] to understand the colossal MCE, or more

extensively to the recent book by A.M. Tishin and Y.I. Spichkin, 2003].

From the here above considerations, it can be expected that the best magnetocaloric

materials in terms of application for refrigeration close to room temperature (RT) must

undergo first order-like magnetic transition easy to handle under rather low magnetic fields

(e.g. 1 to 2 T), with a limited hysteresis effect to be effectively activated reversibly, with a

high density of atom magnetization. Transition metal rich magnetic material such as the T-

pnictides herein reviewed can fulfil these specifications, since they often exhibit tunable both

lattice and ferromagnetic characteristics, moreover being good thermal conductor and formed

with rather inexpensive elements.

Reports with more technical details and systems are available in more specific papers

such as [Lebouc, A. et al. 2005].

IV.2. Magnetocaloric properties in the TT’X series

Up to the 2002 the best promising magnetocaloric material close to room temperature

belong to the series deriving from the Gd5(Si1-xGex)2 type compounds [Pecharsky, V., et al.

1997].
 20

The MnFeP1-xAsx series was revealed by O. Tegus et al [Tegus, O. et al. 2002a] as a

performing magnetocaloric effect (MCE) challenger of the gadolinium intermetallics in terms

of effectiveness, also reference to the cost of elements. Tunability of their MCE

characteristics in interesting temperature range for application was demonstrated soon by the

same group when selecting different compositions by substitution of As to P [Tegus O. et al.

2002b] or of Mn to Fe [Brück, E. et al. 2003, Tegus, O. 2003]. Interestingly high values of

magnetic entropy changes for different compounds of the MnFeP1-xAsx series were measured

up to –ΔSm ~ 35 (J/kgK), in rather moderate applied magnetic field, the temperature of

activation ranging from ~ 150 to 350 K as shown in Figure 13. However, the best

performances remaining a little far from room temperature, better results were recorded close

to RT when substituting a moderate part of Ge to As thus forming MnFeP0.5As0.5-xGex with a

smaller c/a ratio of the hexagonal cell parameter [Brück. E. et al. 2004]. This point revealed

of importance for the corresponding increase of the corresponding so-called Curie

temperature “TC” and amplitude of the magneto-elastic effect at transition. Further, the

maximal magnetic entropy change was derived from little more complicated formulas such as

Mn1.1Fe0.9 P0.7As0.3-xGex [Tegus, O. et al. 2005a]. A more overall analysis of the properties of

the MnFeX series was establish first by E. Brück et al [Brück, E., et al. 2004; Brück, E., et al.

2005a]. Complementary to these specific papers, report was made on the same series of TT’X

materials [Fruchart, D. et al. 2005]. This concerns more particularly systems exhibiting

sensitive magnetic properties with magneto-elastic transitions (Mn1-xCox)2P, Fe(Fe1-xMx)P,

MnRhAs, as well as MnAs.

Besides, a model description of the first order phase transition in MnFeP1-xAsx was

built by the same group [Tegus, O. et al., 2005b] as based on the Bean-Rodbell model.

Another type approach was proposed little earlier [von Ranke, P.J. et al. 2004] based on the

Landau theory as well as in [Zach, R. et al. 1998; Zach, R. 1997] to derive the conditions of a
 21

first order transition and then to evaluate ΔSm and ΔSl, the magnetic and lattice contribution to

change of entropy. All the results look to fit correctly to experimental data [Tegus, O. et al.

2005b; von Ranke, PJ., et al. 2004; Zach, R. et al. 1998; Zach, R., 1997]. However the

electronic part of entropy change at transition ΔSe was not accounted for.

IV.3. Magnetocaloric properties in the TX series

The discovery of giant magneto-caloric effect in MnAs1-xSbx samples was made by

Wada and co-workers and reported in 2001-2002, appears as a major step in the utilization of

T-intermetallics as magnetic refrigerant materials [Wada, H. et al. 2001; Wada, H. et al.

2002]. The magnetic entropy change was rapidly fixed up to – ΔSm ~ 30 J/K kg for x ~ 0.3

[Wada, H. et al. 2003], said unusual characteristics in the vicinity of the first-order phase

transition between the ferromagnetic low-temperature NiAs type structure and the non

magnetic MnP type structure, as illustrated in Figure 2 and 14. Substitution of Sb to As

appeared interesting since this decreases the transition temperature, with a reduction of the

strong hysteresis effect related to the very abrupt character of the first order transition of

MnAs. A theoretical analysis of the giant MCE in MnAs1-xSbx compounds, based on the

Landau theory of phase transition, using a Bean-Rodbell type model, the critical dependence

of the transition temperature 1st vs 2nd order was deduced and also the temperature

dependence of ΔSm was derived in a fair agreement with experience [von Ranke, P.J. et al.

2004]. Then a composite system was anticipated for an optimal design and process to work in

an Erickson mode near RT.

Parallel the effect of deviation from stoichiometry of MnAs1-xSbx materials was

analysed on the magnetic and MCE properties, and excess iron content was related to some

decrease of optimal magnetization level [Morikawa, T. et al. 2004a]. Interstitial iron resulting
 22

from excess composition was proposed as the parameters controlling well “TC”, the nature

(order) of the phase transition, the amplitude of the hysteresis at transition and finally the

force of the MCE, in relation with the increase of the c/a cell parameter ratio. Because of a

certain lack of miscibility with Sb additions, the single phase region was ascribed to

compositions Mn1+δAs1-xSbx with δ ranging from 0.05 to 0.11 [Morikawa, T. et al. 2004b].

Then a specific heat treatment determined to get the best composition and element

distribution, parallel the high value of – ΔSm ~ 34 J/K kg field ranging in [0-5 T], and a

Clausius-Clapeyron analysis (1st order transition) was demonstrated to fit fairly well to the

estimate of – ΔSm plotted vs T built according to the Maxwell relation [Wada, H. et al. 2005].

A further analysis of the heat treatment process was made more recently thus allowing to

determine condition for homogeneous materials with sharp transition [Wada, H. et al. 2006],

when quenching the Mn1+δAs1-xSbx.samples directly from the melt instead of slow cooling

down as done earlier. Besides, using a high pressure resistive furnace (5.5 MPa applied during

synthesis), high quality MnAs samples were prepared [Nascimento, F.C. et al. 2006], thus

exhibiting nicely high variation of entropy, up to – ΔSm ~ 47 J/K kg for 0 to 5 T applied field.

Application of external pressure on MnAs was experienced leading to colossal MCE

levels, the change of entropy at transition exceeding – ΔSm ~ 260 J/K kg from 0 to 5 T under

0.223 GPa as shown on Figure 15, effectively more than 6 times stronger than without

application of pressure [Gama, S. et al. 2004]. From such experiment and analysis, the

authors have concluded that if generally admitted, the assumption of field independence of Δl

and Δe is certainly not valid. Similar pressure experiences were undertaken on well known

Gd5Si2Ge2 type compounds by the same group [Magnus, A. et al. 2005], with a reverse

behaviour for the entropy variation in spite preserving the magnetization level, even

increasing the transition temperature. A complete model allowing describing the colossal

entropy variation of MCE material was developed and specifically applied to MnAs [von
 23

Ranke, P.J. et al. 2006]. It includes the exchange interactions (-parameter), the magneto-

elastic contributions (-parameter), the external pressure effects (via the Grünesein relation,

-parameter), the magnetic field dependence of the lattice entropy, but neglect the electronic

contribution. By adjusting the phenomenological parameters  to experimental results

the model allows to determine the temperature dependence without and under applied field of

the total entropy T. However, the authors consider that if the model does not reproduce

exactly the shape of the T traces versus temperature and pressure, the fair agreement in

amplitude value leads to ascribe the colossal MCE effect to marked increase in the lattice

entropy under pressure. Theoretical analyses of the fundamental behaviour and of the (T, H,

P) phase diagram of MnAs have been made parallel to the experimentations of the S. Gama’s

group by de N.A. Oliveira [de Oliveira, N.A. (2004); de Oliveira, N.A. (2006)].

IV.3. Magnetocaloric properties in other series of pnictides

Other series of intermetallic compounds reveal as well interesting features in terms of

sensitivity to temperature, magnetic field, pressure, chemical composition… ferromagnetic

phases, with first or second order magneto-elastic coupled transitions, as e.g., related to

Mn3GaC, LaSi13-xSix, Ce(Fe1-xCox)2, MnTGe, MnCoSi1-xGex… all different type compounds.

Also in the series of transition metal compounds others families were checked for, as part of

an extended list, e.g. Mn5Ge3-xSbx [Songlin et al. 2002], Mn5-xFeSixSi3 [Songlin et al. 2002],

NdP and NdAs [Plaza, E.J.R. et al. 2004]…with medium to rather high variations of magnetic

entropy at transition. However, the reference book by A.M. Tishin and Y.I. Spichkin [Tishin,

A.M. and Spichkin, Y.I. 2003] exposes deeply the basic concepts and displays unique sets of

data on all of the known systems exhibiting MCE properties. A comparative review of the
 24

main characteristics of the most promising MCE alloys and compounds has been reported

more recently by E. Brücke [Brück, E. 2005b].

Other types of materials are of interest to consider in terms of potentially high ferromagnetic

but switchable properties e.g. the ternary iron germanium pnictides (X = P, As, Sb) where

apart MnP and NiAs type compounds, the systems reveal rich with different types of

structures [Mills, A.M. et al. 2000]

V. CONCLUSION

Two main series of transition metal-rich pnictides, TT’X and TX, reveal a wide panel

of various magnetic properties, but critical situation are made owing strong magneto-elastic

couplings associating crystal structure peculiarities and instabilities of magnetic

configurations. These series recall very attracting with the recent evidence of a marked

magnetocaloric character to the many existing transitions. Presently, the renewed interest

devoted to the TT’X and TX pnictides covers large fields from fundamental analyses up to

performances of materials and systems. In fact the needs of alternating solutions to solve the

double problem of energy and of environment preservation promote strong research efforts,

e.g. for room temperature refrigeration and air conditioning. Anyway, it is worth to note that

exactly 40 years ago, early but determining fundamental characterizations devoted to just

discovered series of transition metal pnictides were thus achieved [Goodenough, J.B. and

Kafalas, J.A. 1967]. This made a milestone lecture of the very unusual physical properties, vs

temperature, magnetic field and pressure, exhibited by the herein discussed series. Needs for a

deeper but detailed knowledge impulse renewed investigations on magnetic pnictides to better

understand the various but interdependent overall contributions to magnetocaloric effect.

 25

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 41

Figures and figure captions

Figure 1: Structures T2, H3 and O4 of the TT’X compounds as projected along axes to
evidence the T (tetrahedral) and P (pyramidal) sites, the latter identified by arrows
toward the apical X site. Above are represented fragments illustrating the triangular
channel hosting the pseudo-rhombohedral TT’X cell.
(R. Fruchart, Ann. Chimie, 1982, vol 7, 6-7, p. 572)

Figure 2: MnAs crystal structures in hexagonal (left) and orthorhombic (right) types.
(F.B. Nascimento, Materials Research v.9, n°1, (2006) p. 113)
 42

Figure 3: Magnetic phase diagram of the system Mn2P – Co2P (after D. Fruchart et al.
Phys. Stat. Sol. (a) 57 675-682).
(Handbook Magnetic Mat., Buschow Ed., vol. 6, O. Beckman & L. Lundgren, p. 236
or D. Fruchart, Phys. Stat. Sol. (a) 57 p. 675-682)

Figure 4: (a) (T,P) phase diagram for Fe2P., (b) (T, t = □) diagram for Fe2-xP, (c)
diagram for (Mn1-xFex)2P, after A. Roger, PhD Thesis, Paris - Orsay (1970).
(or Handbook Magnetic Mat., Buschow Ed., vol. 6, O. Beckman & L. Lundgren, p. 230)

Figure 5: Magnetic phase diagram of the systems CrP – MnP – FeP after Sénateur, J.P.,
et al. (1969).
(or Handbook Magnetic Mat., Buschow Ed., vol. 6, O. Beckman & L. Lundgren, p. 203)
 43

Figure 6a Figure 6b
6a: Phase diagram of the pseudo-binary compounds MnAs1-xPx on the MnAs rich side,
indicating the transition lines from NiAs to MnP type structure, and first order
transition from ferromagnetic NiAs to paramagnetic MnP. 6b: Influence on magnetic
field and pressure on the crystal and magnetic structure of MnAs.
(Handbook Magnetic Mat., Buschow Ed., vol. 6, O. Beckman & L. Lundgren)
(6a: p. 209) (b: p. 205)

Figure 7: Magnetic phase diagram of the MnFeP – MnFeAs system.

(A. Krümbugel-Nylund PhD University of Paris–Orsay, 1974,
or better M. Bacmann et al, J. Magn. Magn. Mat 134, (1994) p. 59 – 67)
 44

a b

Figures 8:
8a: Isothermal MT(B) magnetisation of MnFeP0.5As0.5; 8b: Isofield MB(T) magnetisation
of MnFeP0.5As0.5; 8c: (P,T) magnetic phase diagram of MnFeP1-xAsx, x = 0.275 (TF-AF),
x = 0.3 (“TC”), x = 0.33 (“TC”)
(R. Zach, D. Hab Thesis, Politecknika Krakowska, Zeszyt Naukowy NR 2 Krakow 1997)

Figure 9: The (P-T) phase diagram determined from the present experiment. A
pressure-induced phase transition from the AF(I) to the F takes place at around 5 GPa.
TP was not detected in this experiment. The dotted line was drawn according to
Kanomata T. et al (1987).
(N. Fujii et al, J. Magn. Magn. Mat., 224, 1 (2001) p. 15)
 45

Figure 10 : Mn-Mn interaction curves in MnMX-type intermetallic compounds

calculated from RKKY theory and estimated from refs. [30-32] in Fujii, N., et al (2002)
for Mn alloys. Observation of TC for MnRuP (●), MnRhAs (○), MnZnSb (■) are also
plotted.
(N. Fujii, et al J. Alloys and Compounds, 345 (2002) p. 66)

Figure 11: Experimental magnetic moments of Fe (triangle) and Mn (square) in

tetragonal (T2 – filled symbols) and hexagonal (H3 – empty symbols) structures of
MnFeAs.
(J. Tobola et al, J. Alloys and Compounds 317-318 (2001) p. 279)

Figure 12: Field dependence of the lattice volume per f.u. for MnAs. (○) and (■) indicate
the volume in increasing and decreasing fields, respectively
(F. Ishikawa et al, J. Appl. Phys., 42 (2003) L 920)
 46

Figure 13: Magnetic-entropy change for different compounds of the MnFeP1-xAsx system
for applied field change of 2 and 5 T.
(E. Brück et al, J. Alloys and Compounds, 383 (2004) p. 34)

Figure 14: Magnetization and inverse susceptibility of MnAs showing the temperature
region of different NiAs and MnP crystal structures
(Handbook Magnetic Mat., Buschow Ed., vol. 6, O. Beckman & L. Lundgren, p. 204)
 47

Figure 15: The MCE as a function of temperature and pressure for MnAs
(S. Gama et al PRL 93, 237202 (2004) p. 3)

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