Temperature induced valence instabilities in ternary Eu-pnictides: a comprehensive view

We report on measurements of the lattice constants, magnetic susceptibility, L_III X-ray absorption and Mössbauer-effect on EuNiP and EuPdP, which crystallize in the hexagonal layered Ni₂In structure. In both compounds the Eu valence above 510 K is 2.33. With decreasing temperature they show one (EuPdP) or two (EuNiP) first order phase transitions with a valence increase of about 0.16. At the same time thec-axis shrinks while the a-axis even increases. From Mössbauer measurements we show that the nature of the valence mixing is static. In contrast, the valence mixing in isostructural EuPtP is static at low temperatures, too, but it becomes homogeneous valent above a first order phase transition at 235 K. The behaviour of these compounds (as well as that of EuPdAs) is explained in a new model of electrostatically charged layers. In this model we can explain the temperature dependence of the lattice constants, the static valence mixing and the occurrence of preferred valences of the order 2 6/n. Together with the compression shift model of Hirst we can also understand the mechanism of the phase transitions. A comparison with EuT₂Si₂ compounds in ThCr₂Si₂ structure shows that in EuTX compounds only the electronic structure of the transition elements is relevant for the occurrence of mixed valency.     

Effect of pressure on the valence state of Yb in YbPd2Si2

The intermediate valent behaviour of YbPd₂Si₂ has been studied under pressure in the temperature range from 1.2 K to 90 K by using the 84 keV Mössbauer transition in¹⁷⁰Yb. At 54 kbar and 4.2 K we obtain an increase of the electric field gradient (EFG) by a factor of 3. In addition, the EFG varies strongly with temperature, in contrast to the behaviour at ambient pressure. At 1.2 K a change of the hyperfine pattern is observed indicating a magnetic character of the Yb ion. These results provide evidence of a pressure induced change of the valence state close to 3+.Work supported by the Deutsche Forschungsgemeinschaft     

Mixed valence on dilute Eu in YCu2Si2

We report measurements of electrical resistivity, thermopower, thermal conductivity, magnetic susceptibility, Mößbauer andL _III x-ray absorption of intermediate valent Eu in Y_1–x Eu _x Cu₂Si₂ alloys withx=0.03,x=0.07 andx=0.10. A qualitative comparison of the physical properties of dilute Eu in YCu₂Si₂ with concentrated Eu in EuCu₂Si₂ shows only slight differences; the dominant feature is a very strong variation of the Eu valence with temperature, from about 2.8 at 4 K to about 2.45 at 800 K, in the concentrated compound as well as in the dilute alloys.     

Valence change of europium in the Eu(Ir1−x Pd x )2Si2 silicides

Eu(Ir_1–x Pd _x )₂Si₂ solid solutions which exist only for 0x0.125 and 0.75x1 crystallize in the tetragonal ThCr₂Si₂-type structure. X-ray diffraction data, magnetic susceptibility and¹⁵¹Eu Mössbauer measurements suggest that these compounds can be characterized as homogeneous mixed valence systems. At room temperature and for 0x0.125, the europium valence decreases asx increases. For 0.75x1, a sharp continuous valence transition from Eu²⁺ to Eu³⁺ occurs near 48 K, 54 K and 78 K forx=0.75, 0.81 and 0.94 respectively. These valence changes are discussed in relation with the Eu–(Ir, Pd) interatomic distance.     

Electrical and thermal conductivity of CePd3, YPd3, GdPd3 and some dilute alloys of CePd3 with Y and Gd

Resistivity and thermal conductivity of the intermediate valence compound CePd₃ between 1.3 and 300 K are compared with those of the nonmagnetic and magnetic reference compounds YPd₃ and GdPd₃ and of alloys of the type Ce₁–xRE _x Pd₃ with RE=Y, Gd and 0.01<x<0.5. The analysis reveals the existence of a maximum metallic resistivity of 300 cm for CePd₃. The intrinsic resistivity of CePd₃ rises proportional toT ² up to 100 K, with a coefficientB about 10⁷ times larger than e.g. in copper. We interpret this with indirect electron-electron scattering mediated through valence transitions.     

Transport properties of LaCu2Si2 and CeCu2Si2 between 1.5K and 300K

We report measurements of the electrical resistivity, the thermal conductivityk and the thermoelectric powerS between 1.5K and 300K on the anomalous CeCu₂Si₂ compound and on LaCu₂Si₂ as reference compound. For LaCu₂Si₂ the temperature dependences of andS are in accord with those found in otherd band metals. For CeCu₂Si₂ the observed resistivity (220 µ cm at 200K) leads to a very short electronic mean free path which is of the order of the Ce-Ce spacing. Correspondingly,k is almost identical with the phonon contributionk _p . Below 20K, resistivity and thermoelectric power strongly suggest Fermi liquid behavior with a degeneracy temperature between 20K and 40K. Above 200K, both andS decrease proportionally to –ln(T/1 K).Work performed within the research program of the Sonderforschungsbereich 125 Aachen/Jülich/KölnPart of this work will be presented at the Int. Conf. on Rare Earths in the Metallic State, St. Pierre de Chartreuse, Sept. 1978     

Upper critical magnetic fields of the heavy fermion superconductors CeCu2Si2, UPt3, and UBe13: Comparison between experiment and theory

We report measurements of the upper critical magnetic field,B _c2 (T), on single crystal and polycrystalline samples of the heavy-fermion superconductors CeCu₂Si₂, UPt₃ and UBe₁₃. Comparison is made with experimental results for a conventional superconductor (CeRu₃Si₂) and with results of the weak-coupling theory applied to both ans-wave superconductor in the dirty-limit and ap-wave superconductor. New anomalies are discovered to add to the unusualB _c2 (T) behavior.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

Changes of valence state of Yb in YbCuAl at high pressure: A Mössbauer study

The 84.3 keV Mössbauer transition in¹⁷⁰Yb was used to investigate the intermediate valent intermetallic compound YbCuAl at pressures up to 130 kbar and in the temperature range between 1.6 K and 77 K. The electric quadrupole interaction parameters |eQV _zz | and , as well as their temperature variation are drastically dependent on pressure: |eQV _zz | is at 4.2 K larger by almost a factor of three at 130 kbar when compared to ambient pressure. On the other hand, |eQV _zz | drops by more than a factor of two at 130 kbar when the temperature is raised from 1.6 K to 77 K. A much smaller temperature dependence of quadrupole coupling is present at ambient pressure. Both these effects give strong evidence for a valence transition towards the 4f ¹³ (Yb³⁺) configuration under applied pressure. At 4.2 K this transition is completed near 50 kbar. No magnetic order could be detected down to 1.6 K over the whole pressure range. Some line broadening is observed at high pressures and low temperatures which most probably is related to paramagnetic relaxation phenomena and supports the claim that the Yb ion is in a magnetic state under these conditions.Work supported by the Deutsche Forschungsgemeinschaft     

Gd3+-ESR in the intermediate valent cerium compounds Ce x La1-x Os2

In the intermediate valent compounds Ce _x La_1–x Os₂ the Gd³⁺-ESR shows a non-linear increase of the linewidth H(T) in the temperature range 4.2K<T<300K for 0.3x1.0. This non-linearity of the thermal broadening is strongly altered by changing the Ce-concentration. The experimental results H(T,x) can quantitatively be described via hybridization of conduction electrons with Ce4f electrons: Due to hybridization, the Ce4f states are broadened but remain localized. The conduction electron density of states is reduced in the vicinity of the 4f states. In addition we observe a maximum in the electrical resistivity (T) of CeOs₂ at 270 K.     

Incommensurate and commensurate magnetic long-range order in metallic REPd3 compounds of rare earths (RE=Nd,Tb, Dy,Er, Tm,Yb)

Compared to previous bulk magnetic measurements unusual magnetic ordering phenomena were detected by systematic neutron scattering experiments performed in the temperature range of 7 mKT300 K on the series of cubic metallic compounds REPd₃ of the rare earths RE=Nd, Tb, Dy, Er, Tm and Yb. Except for ErPd₃ withT _N =3 K the observed critical temperatures are compatible with the de Gennes scaling. The complexity of long-range magnetic ordering increases with decreasing 4f ⁿ occupancy, ranging from ferro- or ferrimagnetism in YbPd₃ and DyPd₃ via commensurate antiferromagnetic ordering in ErPd₃ and TmPd₃ [k=(1/2, 1/2, 0)] to incommensurate antiferromagnetic ordering of modulated type in TbPd₃ and NdPd₃. Both RKKY interactions, crystalline electric field, hybridization with 4d states of Pd as well as nuclear spin polarization in the case of RE=Nd appear to be of importance for the magnetic properties of REPd₃ systems.     

Interrelation between electronic structure and interatomic distances for compounds

The heat capacity was studied for LaMn₂Si₂, La_0.75Y_0.25Mn₂Si₂, La_0.7Y_0.3Mn₂Si₂, YMn₂Si₂ and LaFe₂Si₂ isostructural intermetallic compounds in the temperature range 1.8–360 K. The electronic, magnetic and lattice contributions to the heat capacity of the compounds were determined and analyzed. The interrelation was found between values of the electronic contribution to the heat capacity (density of states at the Fermi level) and crystal lattice parameters of R(Mn,Fe,Ni)₂Si₂ compounds. The electronic contribution and the density of states at Fermi level increase with increasing lattice parameters of the compounds. The change of interlayer Mn–Mn exchange interactions with change of Y concentration in La_1-xY_xMn₂Si₂ compounds is not accompanied by considerable changes in the electronic contribution to the heat capacity and density of states at the Fermi level. The performed analysis of the magnetic contribution shows that no essential differences exist between the behavior of the heat capacity of the compounds with d_Mn–Mnd_c and with d_Mn–Mn<d_c upon various types of the magnetic phase transitions.     

Eu valency and recoil-free fraction in EuCo2Si2-x Ge x

The valency of Eu in EuCo₂Si_2-x Ge _x withx=0, 0.5, 1.0, and 2 was determined by¹⁵¹Eu-Mössbauer, Eu-L _III X-ray absorption as well as magnetization studies in the temperature range from 4.1 to 650 K and at external pressures up to 66 kbar. Eu in EuCo₂Si₂ is found to be predominantly trivalent, while in EuCo₂Ge₂ it is divalent. In EuCo₂Si_2-x Ge _x (0x2), two separate narrow Mössbauer absorption lines are observed, corresponding to stable divalent and trivalent Eu ions. In EuCo₂Si_1.5Ge_0.5, the relative spectral areas of the Eu²⁺ and Eu³⁺ Mössbauer lines are found to be strongly temperature and pressure dependent. A decrease in temperature or an application of pressure leads to small changes in the positions of the two absorption lines and to a pronounced increase in the relative spectral area of the Eu²⁺ component. On the other hand, X-ray absorption near-edge structure (XANES) measurements at theL _III threshold of Eu reveal no change in the relative intensity of the Eu²⁺ and Eu³⁺ subspectra as a function of temperature. From these observations it is concluded that the recoil-free fractions of the Eu²⁺ and Eu³⁺ Mössbauer resonances in EuCo₂Si_1.5Ge_0.5 depend in a substantially different way on temperature. With the Debye approximation, Debye temperatures of _D(Eu²⁺)=175 K and _D(Eu³⁺)=250 K are derived. These results clearly show that relative abundances of Eu²⁺ and Eu³⁺ ions may only be derived from Mössbauer linie intensities, if appropriate corrections for differences in recoil-free fraction are applied; this applies even to mixed-valent systems, where Eu ions with different valencies occupy crystallographically equivalent sites.     

Neutron diffraction study of magnetic ordering in PrCu2Si2, PrCu2Ge2, PrFe2Ge2 and NdFe2Ge2

A neutron diffraction study of polycrystalline PrCu₂Si₂ [1], PrCu₂Ge₂ [2], PrFe₂Ge₂ [3] and NdFe₂Ge₂ [4] intermetallics carried out at liquid helium temperature shows the presence of a collinear antiferromagnetic order below T_N = 19 ± 1 K [1], T_N = 16 ± 1 K [2], T_N = 9 ± 1 K [3] and 13 ± 1 K [4]. Magnetic moment, parallel to the c-axis is localized on RE ions only. The magnetic structure of these compounds consists of ferromagnetic layers perpendicular to the c-axis coupled antiferromagnetically with sequence +-+- for PrCu₂Si₂ and PrCu₂Ge₂ and +--+ for PrFe₂Ge₂ and NdFe₂Ge₂. The RE moments amount close to the free ion values for Fe containing compounds but are smaller in those containing Cu suggesting a fairly strong influence of crystal field.     

Magnetic anomalies of thermal expansion in (rare-earth) Ni2 intermetallic compounds

The thermal expansion of eight RENi₂ intermetallic compounds (RE = La, Nd, Sm, Tb, Dy, Ho, Er, Tm) and YNi₂ have been measured between 3.8 and approx. 300 K. The anomalies found at the paramagnetic-magnetically ordered phase transition have allowed an accurate determination of the Curie temperatures. From the low temperature comparison of the thermal expansion of the light RE compounds with that of LaNi₂, and of the heavy RE compounds with that of YNi₂, the Debye temperatures have been obtained. In the case of the compounds DyNi₂, TbNi₂ and HoNi₂ the contributions from crystal field and exchange interactions to the spontaneous volume strain at the magnetically ordered phase have been calculated, the agreement between experiment and calculation being good.     

Mössbauer study of mixed valent silicides Eu(Ir1−x Pd x )2Si2

The solid solutions Eu(Ir_1–x Pd _x )₂Si₂, which exist for 0x0.125 and 0.75x1. cristallize with the tetragonal ThCr₂Si₂-type structure. The variation of the europium valence with composition has been thoroughly studied at temperatures 4.2T293 K by¹⁵¹Eu Mössbauer resonance. For 0x0.125 the europium valence at room temperature decreases asx increases. For 0.75x1 the valence transition temperature Eu³⁺Eu²⁺ increases asx increases.     

Magnetic relaxation spectra of YbPd2Si2

We present the results of inelastic neutron scattering experiments on the intermediate-valent system YbPd₂Si₂ to investigate the magnetic relaxation behaviour. We have performed measurements on polycrystalline samples with neutrons of incident energyE ₀=3.1 meV at temperatures between 1.5 K and 250 K, and withE ₀=12.7 meV andE ₀=50.8 meV at temperatures between 5 K and 50 K using time-of-flight spectrometers. At temperaturesT>50 K we find a pure quasielastic magnetic response with a rather broad linewidth typical for intermediate-valent systems. AtT50 K an inelastic excitation line appears at about 21 meV; its intensity increases with decreasing temperature. In the same temperature range (T<50 K) the quasielastic linewidth decreases rapidly and atT=5 K the quasielastic response has been apparently transformed to a second inelastic feature at about 4.7 meV. The width of this low-energy excitation fits well to the temperature dependence of the quasielastic linewidth forT>5 K.     

ESR of Gd-impurities in the heavy fermion compounds CeCu2Si2 and CeAl3

The heavy fermion systems CeCu₂Si₂ and CeAl₃ are characterized by a huge quasiparticle density of states responsible for the large electronic specific heat. The observation of a Gd³⁺ electron spin resonance (ESR) in single crystals CeCu₂Si₂ and in polycrystalline CeAl₃ clearly demonstrates the local character of these quasiparticles. Nevertheless, the Gd-spin relaxation shows remarkable anomalies with respect to the isostructural compounds LaCu₂Si₂ and LaAl₃: Probably via RKKY coupling, Ce 4f-spin fluctuations give rise to an enhanced Gd-spin relaxation resulting in an unusual non-linear thermal broadening around the Kondo temperature. From this we obtain information about the temperature dependence of the Ce 4f-spin correlation time.     

Magnetic properties and structural chemistry of ternary silicides (RE,Th, U)Ru2Si2 (RE = RARE EARTH)

Ternary silicides (RE, Th, U)Ru₂Si₂ have been synthesized from the elements. All the compounds (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were found to be isotypic and to crystallize with the structure type of ThCr₂Si₂ (ordered derivative of the BaAl₄-type). The magnetic behavior of these alloys was studied in the temperature range 1.5 K < T < 1100 K. Magnetic susceptibilities at temperatures T > 300 K closely follow a typical Van Vleck paramagnetism of free RE³⁺-ions. In the case of CeRu₂Si₂ susceptibilities are well described for 20 K < T < 1100 K by a Van Vleck paramagnetism of widely spaced multiplets; the observed effective paramagnetic moment μ_eff = 2.12 BM indicates a high percentage (85%) of Ce³⁺. SmRu₂Si₂ yields an effective moment μ_eff = 0.54 BM, which compares reasonably well with the Hund's rule J = 5/2 ground level for free Sm⁺ and a low-lying excited level with J = 7/2. For temperatures T > 15 K the magnetic susceptibility as a function of temperature follows the “Van Vleck behavior” for free Sm³⁺. At low temperatures ferromagnetic ordering was encountered for (Pr, Nd, Ho, Er, Tm)Ru₂Si₂, whereas antiferromagnetic ordering was observed for (Sm, Gd, Tb, Dy)Ru₂Si₂. The ordering temperatures are generally below 55 K. No superconductivity was found for temperatures as low as 1.8 K.     

Combined Mössbauer and LIII-edge X-ray absorption study of mixed- valent EuPd2Si2 and EuNi2P2

The mean valence of Eu is determined by L_III-edge X-ray absorption (L_III-XA) and ¹⁵¹Eu Mössbauer isomer shift measurementd for the mixed-valent compounds EuPd₂Si₂ and EuNi₂P₂ in the temperature range from 1.7 to 300 K. For EuPd₂Si₂, the behaviour of the satellite line observed in the Mössbauer spectra was investigated in detail. From a comparison of the L_III-Xa and Mössbauer results obtained on identical samples the valence/isomer shift calibration problem as well as possible final-state effects in L_III-XA spectra are discussed.