# Anomalous Low Temperature States in CeNi2Ge2

## I Introduction

Strongly correlated electron materials in general and the heavy fermion compounds in particular exhibit unusual metallic states and low temperature phase transitions that remain only partly understood. The temperature dependences of the thermodynamic and transport properties, and in particular of the resistivity, allow us to identify a number of apparently distinct regimes. At high temperatures, a weakly temperature dependent, large resistivity consistent with scattering from thermally disordered local magnetic moments is observed down to an upper temperature scale, $`T_{sf}`$ . Below $`T_{sf}`$, the resistivity drops with decreasing temperature and in the absence of a phase transition the resistivity and other bulk properties follow the predictions of Fermi liquid theory below a lower temperature scale $`T_{FL}`$. The range between $`T_{FL}`$ and $`T_{sf}`$, sometimes described as a spin liquid regime, appears as a narrow cross-over region in most materials.

An increasing number of systems are coming to light, however, in which - due to their proximity to magnetic phase transitions - the Fermi liquid regime is suppressed to very low temperatures or even masked by the onset of superconductivity or other forms of order (see e.g. ). The unconventional normal states observed in these metals might be examined in the first instance in terms of phenomenological models for the fluctuations of the local order parameter, i.e. the local magnetisation for ferromagnetism and the local staggered magnetisation for antiferromagnetism , or of some associated variable. If the magnetic ordering temperature is suppressed to absolute zero, these modes soften over large portions of reciprocal space at low temperatures, leading to a strong enhancement of the quasiparticle scattering rate and potentially to a breakdown of the Fermi liquid description in its simplest form. This breakdown may be expected to be particularly apparent in the temperature dependence of the resistivity $`\rho (T)`$ that may deviate from the usual Fermi liquid form $`\rho (T)T^2`$ in pure samples at low temperatures.

To look for a breakdown of the Fermi liquid description in pure materials as opposed to the more extensively studied doped  heavy fermion systems, we have selected stoichiometric compounds that are close to being magnetically ordered at low temperature and have used hydrostatic pressure to tune these compounds through quantum ($`T0K`$) phase transitions.

The systems that we have selected, namely the isostructural and isoelectronic relatives CePd<sub>2</sub>Si<sub>2</sub> and CeNi<sub>2</sub>Ge<sub>2</sub>, allow for examinations of an antiferromagnetic quantum critical point in pure metals for the first time in considerable detail. CeNi<sub>2</sub>Ge<sub>2</sub> and CePd<sub>2</sub>Si<sub>2</sub> are isostructural to the heavy fermion superconductor CeCu<sub>2</sub>Si<sub>2</sub>  and its larger volume relative CeCu<sub>2</sub>Ge<sub>2</sub>  (both with the ThCr2Si2 structure), but differ from CeCu<sub>2</sub>Si<sub>2</sub> in the number of d electrons in the d-metal constituent, and hence in the character of the Fermi surface and in the magnetic properties.

At ambient pressure, CePd<sub>2</sub>Si<sub>2</sub> orders in an antiferromagnetic structure with a comparatively small moment of 0.7 $`\mu _B`$ below a Néel temperature $`T_N`$ of about 10 K , which falls with increasing pressure . The spin configuration consists of ferromagnetic (110) planes with spins normal to the planes and alternating in direction along the spin axis. In a recent study , we have elucidated the phase diagram of CePd<sub>2</sub>Si<sub>2</sub> up to hydrostatic pressures of about 30 kbar. The Néel temperature has been found to drop linearly with pressure above 15 kbar and to extrapolate to zero at a critical pressure, $`p_c\text{28 kbar}`$, while the shoulder in the resistivity, $`T_{sf}`$, shifts from 10 K at low pressure to about 100 K near $`p_c`$. Superconductivity appears below 430 mK in a limited pressure region of a few kbar on either side of $`p_c`$. This behaviour, and perhaps that in a related system CeRh<sub>2</sub>Si<sub>2</sub> , is believed to be consistent with an anisotropic pairing arising from magnetic interactions . Here, we concentrate on the striking normal state behaviour of the resistivity, which deviates strongly from the $`T^2`$ form usually associated with a Fermi-liquid (upper curve in Fig. 1 and left inset in Fig. 2). The range between $`T_{sf}`$ and $`T_{FL}`$, in many materials a narrow cross-over regime, thus appears to open up to more than two orders of magnitude in temperature and becomes the dominant feature of the system, exposing the intervening spin liquid state for closer scrutiny.

The electronically and structurally equivalent compound CeNi<sub>2</sub>Ge<sub>2</sub> , which is of central interest here, has a slightly smaller lattice constant and its zero pressure behaviour may be expected to be similar to that of CePd<sub>2</sub>Si<sub>2</sub> at a pressure close to but higher than $`p_c`$.

## II Results

As shown in Fig. 1, high purity samples of CeNi<sub>2</sub>Ge<sub>2</sub> at ambient pressure and of CePd<sub>2</sub>Si<sub>2</sub> at $`p_c`$ exhibit qualitatively similar anomalous temperature dependences of the resistivity.

For CePd<sub>2</sub>Si<sub>2</sub> near $`p_c`$, the resistivity has a form $`\rho =\rho _0+AT^x`$ with an exponent $`x`$ close to 1 over a wide range, from the onset of superconductivity near 0.4 K up to about 40 K (left inset of Fig. 2). Experiments carried out on various samples and different sample orientations have revealed a variation of the exponents in the range $`1.1<x<1.4`$ and a general trend towards lower values for purer (lower $`\rho _0`$) specimens, indicating a possible limiting value of close to 1 for ideally pure samples (inset of Fig. 1).

Our present measurements at ambient pressure show that CeNi<sub>2</sub>Ge<sub>2</sub> follows a similar power law variation of the resistivity over at least an order of magnitude in temperature above about 200 mK and up to pressures of at least 17 kbar (Fig. 1). We have extended this study to lower temperatures under applied magnetic fields in a high quality sample, which showed no sign of a superconducting transition down to 100 mK at 0.5 T and above. At 0.5 T, a detailed analysis of the temperature dependence of the power-law exponent (more precisely, the logarithmic derivative defined in the caption of Fig. 2) reveals a rapid cross-over to the Fermi-liquid value $`x=2`$ below a temperature $`T_{FL}\text{200 mK}`$ (Fig. 2). This cross-over region rises and broadens with increasing magnetic field (Fig. 2).

These findings indicate that CeNi<sub>2</sub>Ge<sub>2</sub> is delicately placed close to the critical point studied in CePd<sub>2</sub>Si<sub>2</sub> at high pressure, returning to Fermi liquid behaviour at low temperatures as the spin fluctuations are quenched by an increasing magnetic field.

One sample of CeNi<sub>2</sub>Ge<sub>2</sub> shows a complete loss of resistance at ambient pressure below 200 mK (Fig. 3), similar to the occurrence of superconductivity in high pressure CePd<sub>2</sub>Si<sub>2</sub>, while a number of other high quality crystals exhibit a drop in $`\rho (T)`$ of about 85% at low temperatures. We note that a downturn of approximately 10% in the resistivity of CeNi<sub>2</sub>Ge<sub>2</sub> below 100 mK is also evident from data in . A study of the shift of this transition in a second sample with magnetic field yields an initial slope $`dB_{c2}/dT5T/K`$ (inset of Fig. 3), comparable with the value of $`6T/K`$ observed for the superconducting transition in high-pressure CePd<sub>2</sub>Si<sub>2</sub> . The transition is very sensitive to hydrostatic pressure (inset of Fig. 3) and above 4 kbar, no drop of the resistivity is observed. The resulting phase diagram is reminiscent of the behaviour of CePd<sub>2</sub>Si<sub>2</sub> at high pressure and is consistent with our conjecture that CeNi<sub>2</sub>Ge<sub>2</sub> is a smaller volume relative of CePd<sub>2</sub>Si<sub>2</sub>.

Further anomalies were discovered at still higher pressure in CeNi<sub>2</sub>Ge<sub>2</sub>, which showed indications of a new ordered phase (labelled $`T_x`$ in Fig. 4) at around 1 K and, again, a drop of resistance of up to 100% below about 0.4 K ($`T_s`$ in Fig. 4), reminiscent of superconductivity. We note that early measurements of the specific heat in the same region of the phase diagram have revealed an anomalous peak, which may be associated with our upper transition at $`T_x`$ . In contrast to the superconducting phase found in high pressure CePd<sub>2</sub>Si<sub>2</sub> and to the corresponding low pressure phase in CeNi<sub>2</sub>Ge<sub>2</sub>, these high pressure states in CeNi<sub>2</sub>Ge<sub>2</sub> are relatively insensitive to variations of lattice density. In this sense they are reminiscent of the behaviour observed in CeCu<sub>2</sub>Si<sub>2</sub>, where a superconducting phase persists over a wide region of pressure up to about 100 kbar .

## III Discussion

In both CeNi<sub>2</sub>Ge<sub>2</sub> and CePd<sub>2</sub>Si<sub>2</sub>, the temperature dependence of the resistivity is characterised over a wide range by a power-law with exponent close to 1, and by rapid cross-overs to the high and low temperature forms. This behaviour is not limited to a critical lattice density alone, but, at least in CeNi<sub>2</sub>Ge<sub>2</sub>, appears to extend over a considerable range in pressure. These properties of our two tetragonal metals contrast sharply with that of the cubic antiferromagnet CeIn<sub>3</sub> . In the latter the resistivity deviates from the Fermi liquid form only in a very narrow pressure range near the critical pressure $`p_c`$ where $`T_N\text{0 K}`$. At $`p_c`$ and in low magnetic fields the resistivity exponent, or more precisely $`d\mathrm{ln}(\rho \rho _0)/d\mathrm{ln}T`$, grows smoothly with decreasing temperature and tends towards a value of about $`3/2`$ at around 1 K.

We now consider to what extent these findings may be understood in terms of the standard model for spin fluctuation scattering. In this model, the resistivity is given essentially by the population of spin excitations that is proportional to an effective volume $`q_T^d`$ in reciprocal space centred on the ordering wavevector $`𝐐`$. Here $`d`$ is the spatial dimension and $`q_T`$ is a characteristic thermal wavevector that is proportional to $`T^{1/z}`$, if the spin fluctuation rate $`\mathrm{\Gamma }_{𝐐+𝐪}`$ at a wavevector $`𝐐+𝐪`$ varies as $`q^z`$ at a small $`q`$ and at $`p_c`$. For the simplest case, $`z=2`$ and thus the resistivity is predicted to vary as $`T`$ for $`d=2`$ and $`T^{3/2}`$ for $`d=3`$ far below $`T_{sf}`$ and at $`p_c`$, when antiferromagnetic order vanishes continuously . These results are qualitatively consistent with experiment, if we take $`d=3`$ for cubic CeIn<sub>3</sub>, and if the effective dimension is closer to 2 for tetragonal CePd<sub>2</sub>Si<sub>2</sub> and CeNi<sub>2</sub>Ge<sub>2</sub>. The latter assumption is not necessarily inconsistent with the known magnetic structure of CePd<sub>2</sub>Si<sub>2</sub>, that suggests a frustrated spin coupling along the c-axis and hence a strongly anisotropic spin fluctuation spectrum .

There are at least two major difficulties with this description. Firstly, it assumes that essentially all carriers on the Fermis surface scatter strongly from excited spin fluctuations. This assumption, however, cannot be justified within the usual Born approximation in the presence of harmonic spin fluctuations in an ideally pure system. Under these conditions, those carriers not satisfying the ‘Bragg’ condition for scattering from critical spin fluctuations near $`𝐐`$ are only weakly perturbed and at low T lead to a Fermi liquid $`T^2`$ resistivity and not to the above anomalous exponents . Secondly, for the standard form assumed for the temperature and pressure dependence of $`\mathrm{\Gamma }_{𝐐+𝐪}`$ the model of the last paragraph predicts (i) a gradual increase of $`d\mathrm{ln}\rho /d\mathrm{ln}T`$ with decreasing $`T`$ tending to the limiting exponent only for $`TT_{sf}`$, and (ii) a rapid cross-over to the Fermi liquid exponent at low T as a function of pressure (or when the magnetic transition is not continuous). Neither of these predictions appear to be consistent with our findings in CePd<sub>2</sub>Si<sub>2</sub> and CeNi<sub>2</sub>Ge<sub>2</sub>.

The first of these two difficulties may perhaps be cured by including the effects of residual impurities, spin fluctuation anharmonicity, and corrections to the Born approximation that may homogenise the quasiparticle relaxation rate over the Fermi surface. The second problem might be resolved by means of a more realistic model for the temperature and pressure dependences of $`\mathrm{\Gamma }_{𝐐+𝐪}`$ than that currently employed. A first step towards such refinements has recently been proposed, specifically for the effects of residual impurities , but it is too early to tell whether or not it can account for all of the features we observe, both in our tetragonal and the cubic systems, in a consistent way.

We also point out that a description of CePd<sub>2</sub>Si<sub>2</sub> and CeNi<sub>2</sub>Ge<sub>2</sub> based on a more extreme separation of charge and spin degrees of freedom than is present in current approaches, cannot be ruled out . A complete theory would have to account not only for the differences between our tetragonal and cubic systems and the unexpectedly wide range of apparent criticality in CePd<sub>2</sub>Si<sub>2</sub> and CeNi<sub>2</sub>Ge<sub>2</sub>, but also for the occurrence of superconductivity on the border of antiferromagnetism in all of these cases, and the higher pressure phases that we observe in CeNi<sub>2</sub>Ge<sub>2</sub>.

## IV Conclusion

The 4f-electron metals CeNi<sub>2</sub>Ge<sub>2</sub> and CePd<sub>2</sub>Si<sub>2</sub> offer the possibility of observing an unconventional normal state over a wide window in temperature and pressure without chemical doping. The similarity between the two materials suggests that CeNi<sub>2</sub>Ge<sub>2</sub> at ambient pressure is conveniently placed very close to the antiferromagnetic quantum critical point, as studied under high pressure in CePd<sub>2</sub>Si<sub>2</sub>, and make it an attractive material for future investigations. The fixed value of the power-law exponents over a wide range in temperature - reminiscent of the behaviour observed in some of the high T<sub>c</sub> oxides - and the wide pressure range of apparent criticality appear to defy a description in terms of the spin fluctuation model in its simplest form.

Superconductivity in rare-earth based heavy fermion metals is an uncommon phenomenon. CeNi<sub>2</sub>Ge<sub>2</sub> may be the second ambient pressure superconductor in this class after CeCu<sub>2</sub>Si<sub>2</sub>, if the zero-resistance state observed at low pressures can be identified as superconductivity. The pairing mechanism in CePd<sub>2</sub>Si<sub>2</sub> and CeNi<sub>2</sub>Ge<sub>2</sub>, in which superconductivity exists only close to the very edge of antiferromagnetic order, may however be different from that in CeCu<sub>2</sub>Si<sub>2</sub> . On the other hand, the high pressure, zero-resistance state in CeNi<sub>2</sub>Ge<sub>2</sub> could offer a new perspective for our understanding of the first heavy fermion superconductor, CeCu<sub>2</sub>Si<sub>2</sub>.

###### Acknowledgements.

We thank, in particular, P. Coleman, J. Flouquet, P. Gegenwart, C. Geibel, I. Gray, S. Kambe, D. Khmelnitskii, F. Kromer, M. Lang, A. P. Mackenzie, G. J. McMullan, A. J. Millis, P. Monthoux, C. Pfleiderer, A. Rosch, G. Sparn, F. Steglich, A. Tsvelik and I. R. Walker. The research has been supported partly by the Cambridge Research Centre in Superconductivity, headed by Y. Liang, by the EPSRC of the UK, by the EU, and by the Cambridge Newton Trust.