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# Superconducting properties of RuSr2GdCu2O8 studied by SQUID magnetometry

## I Introduction

Since its first observation, high temperature superconductivity (HTSC) is a fascinating and very active field of research. The paper of J. G. Bednorz and K. A. Müller Bednorz  triggered a race for higher superconducting transition temperatures, Tc, which led to the discovery of many new superconductors. All these compounds though, had a common feature: A layered structure, where the existence of CuO2 layers seemed to be essential for the observation of superconductivity, at least until recently Maeno . Because of this feature, the term Cuprates is very often used to describe the HTSC compounds and distinguish them from the elemental or more conventional superconductors described by the BCS theory Bardeen .

Although there is no complete theory explaining the superconductivity of the cuprates, the CuO2 layers are believed to be responsible for conductivity and superconductivity, while interspersed layers, either insulating or weakly metallic, act as charge reservoirs donating carriers to the CuO2 planes. Thus, the cuprates can be viewed as a stacking of superconducting sheets (consisting of the CuO2 layers) coupled by Josephson interaction.

There appears to exist a relation between the maximum Tc of a cuprate and the number of the CuO2 layers per superconducting sheet. For example books , La2-xMxCuO4 with M = Ba, Sr, Ca and one CuO2 layer per superconducting sheet have a Tc of about 30 K, RBa2Cu2+mO6+m with R = Y, La, Nd, Sm, Eu, Ho, Er, Tm, Lu and two CuO2 layers per superconducting sheet have a Tc of the order of 90 K, while Bi2Sr2Can-1CunO2n+4 and Tl2Ba2Can-1CunO2n+4 with n = 3 and three CuO2 layers per superconducting sheet have a Tc of about 110 and 125 K respectively. Thus, the more CuO2 layers per superconducting sheet the higher the maximum Tc.

With this empirical relation in mind, it is interesting to investigate how the properties of a two-layer system, like YBa2Cu3O6+x (YBCO), would be affected, if the coupling between the superconducting sheets is changed, with the introduction of a metallic block. An effort to follow this idea made by L. Bauernfeind Bauernfeind1  led to the discovery of RuSr2GdCu2O8 (Ru-1212) Bauernfeind2 ; Bauernfeind3 , where the (Ba,O)-(Cu,O)-(Ba,O) charge reservoir of YBCO is substituted by a SrRuO3-like block. SrRuO3 is a pseudocubic perovskite and a metallic itinerant ferromagnet with TCurie $``$ 160 K Klein .

The Tc of Ru-1212 depends strongly on the preparation conditions McLaughlin  and there are reports for non-superconducting samples Felner1  as well as for samples, in which the onset of superconductivity reaches 50 K Bauernfeind1 ; Bernhard1  or even higher for Ru/Cu substitutions Klamut2 . In any case, it is low compared to that of YBCO, presumably because of the underdoped character of the CuO2 planes. Powder neutron diffraction studies Chmaissem ; Lynn ; Jorgensen  showed, that the Ru (and Gd) moments in this compound order antiferromagnetically at $``$ 135 (2.5) K. In more detail, a canted arrangement of the moments is indicated by hysteresis loops in d.c. magnetization vs. magnetic field measurements Bernhard2 ; Jorgensen , which reveal a ferromagnetic component in the compound’s magnetic properties (weak ferromagnetism). The fact that Ru-1212 is magnetic, is not surprising, in view of the properties of SrRuO3 mentioned above, but makes the family of Ru-1212 compounds Williams ; Takagiwa ; Hai , together with RuSr2(R0.7Ce0.3)2Cu2O10 Bauernfeind4 ; Felner2 ; Chen ; Ren , where R = Eu, Gd (Ru-1222), the only family of HTSC compounds, where superconductivity arises in a state, in which magnetic order is already developed.

There is some skepticism, especially whether superconductivity is a bulk property of Ru-1212, or even an intrinsic property of this compound at all. Xue et al. Xue  report the absence of a Meissner state for Ru-1212, while Chu et al. Chu  suggest the existence of a crypto-superconducting structure in this compound. On the other hand, heat capacity Tallon , together with Muon Spin Rotation Bernhard2  and Electron Spin Resonance experiments Fainstein  indicate, that bulk superconductivity and magnetism in Ru-1212 coexist on a microscopic scale.

The skepticism, whether Ru-1212 is a bulk superconductor or not, is enhanced by the controversial results on the field cooled d.c. magnetization of Ru-1212 and related compounds published by different groups. Field expulsion shown in such a measurement, corresponding to a bulk Meissner effect, is generally considered as the key indicator for bulk superconductivity. Nevertheless, some published data include an increase of the magnetization at the temperature where intergranular coupling has been established Klamut2 , sometimes followed by a decrease of the magnetization at lower temperatures, which leads to the appearance of a peak in the magnetization vs. temperature plots Papageorgiou . Klamut et al. Klamut1  have tentatively attributed these features to a change of the magnetic ordering of the Ru sublattice upon entering the superconducting state or to an anomalous flux lattice behavior. Artini et al. Artini  and Bauernfeind Bauernfeind1  report a rather “reversed” effect, where a decrease of the magnetization is observed first, attributed to a Meissner behavior, followed by an increase of the magnetization at lower temperatures. Artini et al. Artini  attribute the poor visibility of the Meissner state to the existence of a spontaneous vortex state proposed by Bernhard et al. Bernhard1  or to a phase-lock of an aggregation of small Josephson-coupled superconducting grains or domains proposed by Chen et al. Chen . The field cooled curve of Klamut et al. Klamut1 , with an increase of the magnetization just below Tc, followed by a plateau at low temperatures is also reminiscent of a “reversed” effect compared to the field cooled curves published by Bernhard et al. Bernhard1 , which show a decrease of the magnetization just below Tc and a plateau at low temperatures, considered as evidence for the existence of a bulk Meissner state in Ru-1212.

In their paper, Artini et al. Artini  recognize that the complexity of the magnetic signal of Ru-1212, which consists of contributions from the Gd paramagnetic spin lattice, the Ru spin lattice and the diamagnetic signal due to superconductivity, can drastically affect the quality of a SQUID magnetization measurement, if this is done in a non-uniform field. Indeed, the different behaviors of the field cooled d.c. magnetization of Ru-1212 described above are reminiscent of features reported by McElfresh et al. McElfresh  for an YBCO film measured in different (measured) field profiles. These features though, the specific characteristics of which depended on the profile of the measuring field, did not represent intrinsic properties of the sample. They did arise from the fact, that the magnetization of the sample was changing, because of the non-uniform field, during a measurement at fixed temperature, while the algorithms used by the magnetometer’s software to calculate the magnetization assume that this does not happen. It is the purpose of this paper to investigate whether Ru-1212 shows a similar sensitivity to field inhomogeneities, which could give rise to experimental artefacts, during a SQUID d.c. magnetization measurement.

## II Experimental

### II.1 Sample preparation and characterization

Polycrystalline samples of Ru-1212 were prepared following a two-step procedure proposed by Bauernfeind et al. Bauernfeind1 ; Bauernfeind3 . First, Sr-2116 was prepared from stoichiometric quantities of RuO2, Gd2O3 and SrCO3. The mixed powders were ground, calcined at 950 C in air, reground, milled, pressed into pellets and fired for 16 h at 1250 C in air. In a second step, the obtained Sr-2116 was mixed with CuO and the mixture was ground, milled, pressed into pellets and fired for 120 h at 1060 C in flowing oxygen.

A Seifert XRD 3000 P diffractometer was used for the sample characterization. The powder diffraction data were recorded for 40 seconds at each 2$`\theta `$ in steps of 0.01 from 5 to 75. A weak peak indicative of SrRuO3 trace impurities was detected in the pattern of the sample.

### II.2 Measurements

Resistance measurements were performed with a standard four-probe a.c. technique (at 22.2 Hz) on bar-shaped pieces cut from the pellets using silver paint contacts.

a.c. susceptibility measurements were done with a home-made susceptometer using a standard lock-in technique at 22.2 Hz with different field amplitudes.

d.c. magnetization measurements were done with a commercial SQUID magnetometer (Cryogenic Consultants Ltd. S600) in the temperature range 7 K $``$ T $``$ 200 K and magnetic fields B $`<`$ 10 mT. In order to overcome the problem of remanent fields, we used paramagnetic samples with high magnetic moments in low fields (e.g. PrCu6) as field sensors. The magnet power supply was disconnected and an external current source (Knick DC-Current-Calibrator J152) was used to apply the appropriate current for the cancellation of the remanent field according to the signal from the paramagnetic sample. Complete cancelation is difficult to be achieved, but after this procedure, values for the magnetic moment of the paramagnetic samples close to the resolution of our SQUID (5$``$10-10 Am2) were recorded at 7 K. Comparing this signal with that at the same temperature in a field of 92.9 mT we estimate a remanent field of 1.5 $`\mu `$T. The low fields of figures 2 and 3 were also determined by a comparison of the paramagnetic sample’s signal at 7 K with that at the same temperature in a field of 92.9 mT. Nevertheless, since our measurements indicate that field inhomogeneties were present, the given field values should be considered as estimates. For this reason, when a comparison between measurements in a certain field was necessary, the samples were measured one after the other, before any change of the field was undertaken.

## III Results and discussion

### III.1 Superconductivity and magnetism of our Ru-1212 sample

Figure 1 and figure 2 show the a.c. susceptibility, resistivity, as well as the zero field cooled (z.f.c) and field cooled (f.c.) d.c. magnetization curves of our Ru-1212 sample. A magnetic transition is observed, as expected Chmaissem ; Lynn ; Jorgensen , at 135 K. The hysteresis between the z.f.c. and f.c. branch of the d.c magnetization probably arises from the canting of the antiferromagnetically ordered Ru moments Felner1 . Increased canting of the Ru moments due to the presence of the external magnetic field in the f.c. process leads to higher values of the magnetization compared to the z.f.c. branch. The resistance of the sample, which has a metallic behavior at high temperatures, shows a cusp in the temperature range of the magnetic transition. The onset of superconductivity is at 50 K, while the resistance becomes zero at 30 K. At this temperature, the inter-granular coupling is established and a clear diamagnetic response is observed in the real part of the a.c. susceptibility with the corresponding loss peaks in the imaginary part. Typical for shielding due to inter-granular coupling, the transition widens and shifts to lower temperatures, as the a.c. field amplitude is increased Widder .

Distinct anomalies of the d.c. magnetization are observed for our Ru-1212 sample as it enters the superconducting state. The curves presented in figure 2 show a clear increase at 25 K and a peak at a temperature of 18 K, below which a magnetization decrease indicative of field expulsion due to superconductivity begins. Klamut et al. Klamut1  were, to the best of our knowledge, first to report similar features. Their sample had a higher Tc of 35 K and the peak was observed above 25 K under the condition of zero field cooling. The origin of these peaks is still unclear. A comparison of figure 1 with figure 2 shows, that the onset of the peaks ($``$ 25 K) is close to the temperature, where intergranular coupling has been established. Thus, the increase of the magnetization happens when shielding currents start to flow between the grains. This fact was also observed by Klamut et al. Klamut1 .

Figure 3 shows the behavior of the low temperature Ru-1212 magnetization peak in different magnetic fields. The position of the peak ($``$ 18 K) does not change significantly with magnetic field up to 3.6 mT. Above this field value, the feature is washed out and the Gd paramagnetic contribution seems to dominate at low temperatures. In these higher fields the Gd contribution becomes more significant also at higher temperatures, in the normal state of the sample.

In the following, we will investigate the origin of these features. We will examine first though, whether the observed behavior of the Ru-1212 magnetization at low temperatures is not related to impurities.

### III.2 Can the peaks be due to Sr2GdRuO6 trace impurities ?

The d.c. magnetization of Sr2GdRuO6 (Sr-2116) is shown in figure 4. Sr-2116 can appear as an impurity phase in the Ru-1212 matrix and in cases like ours, is used as a precursor for the preparation of Ru-1212 Bauernfeind1 ; Bauernfeind3 ; Bernhard2 . The sample was prepared as described in the first step of the Ru-1212 preparation. In the X-ray pattern traces of the original Gd2O3 powder were still present. The specific features of the Sr-2116 magnetization were presented and analysed in our previous work Papageorgiou  and will not be discussed here. It is interesting to note, that Sr-2116 shows a magnetization peak around 18 K, i.e., in the temperature range, where the peaks for Ru-1212 are observed.

In figure 4a, measurements on bulk samples of Ru-1212 and Sr-2116 are shown. The results for Ru-1212 presented in figure 4a and those in the previous figures are on two different pieces of Ru-1212 coming from the same pellet. All the necessary quantities for a comparison between the two compounds are given in the figure caption: the height of the peaks in units of magnetic moment and the masses of the samples. Although our X-ray data put an upper limit of about 0.3 mg to possible Sr-2116 impurities in our Ru-1212 sample, which represents a concentration of about 3 % (resolution of the instrument), it is obvious, that $``$ 9 mg, or 88 %, of Sr-2116 impurities would be needed to quantitatively explain the magnetization peak of the Ru-1212 sample as arising due to Sr-2116.

Similar argumentation was used in our previous work Papageorgiou  to exclude the possibility that the peaks observed for Ru-1212 are due to Sr-2116 impurities. The fact though, that possible Sr-2116 grains are enclosed in a magnetic Ru-1212 matrix was not taken into account. We do not expect, that the magnetism of Ru-1212 would affect the behavior of Sr-2116 significantly when the sample is cooled in a small applied field of 0.25 mT, like in the case presented in figure 4. Assuming a homogeneous Ru-1212 matrix and using the magnetization M at 25 K for the bulk Ru-1212 sample from figure 4a, we estimate a contribution to the magnetic field from the Ru-1212 compound B = $`\mu _0`$$``$M = 0.2 mT, which could not enhance the magnetism of small amounts of Sr-2116, not visible in X-ray powder diffraction patterns, distributed in the Ru-1212 matrix to the level of the Ru-1212 peaks.

We have already discussed Papageorgiou  how parameters, which can be affected during the preparation of Sr-2116, like oxygen content, Ru deficiencies or Cu doping (this could take place for example during the preparation of Ru-1212 by adding CuO to Sr-2116), could enhance the magnetism of Sr-2116 and then smaller amounts of this compound would be necessary to produce the peaks measured for Ru-1212. Indeed, the Sr-2116 peaks we found previously Papageorgiou  were more pronounced compared to those of figure 4. These points make the above quantitative comparison somewhat uncertain. However, in none of the cases we studied Papageorgiou , did we find a peak for Sr-2116-like compounds, which could explain the Ru-1212 peak, assuming an impurity level consistent with our X-ray data.

In order to further investigate whether the magnetization anomalies in the superconducting state of Ru-1212 are due to Sr-2116 impurities or not, we powdered the samples of Ru-1212 and Sr-2116 of figure 4a and remeasured their magnetization. The powders were embeded in GE varnish for the measurements. The result is shown in figure 4b. The powdered Ru-1212 sample has a completely different behavior at low temperatures. The peak has dissappeared together with the magnetization decrease indicative of field expulsion due to superconductivity. This behavior can be attributed to grain size of the order of the penetration depth or to the quasi-two-dimensional character of the superconducting regions Klamut2  which prevents intragrain flux expulsion to occur. On the other hand, the properties of Sr-2116 remain unchanged after powdering. Thus, if the Ru-1212 peak was due to Sr-2116 impurities, we expect it to still be present in the powdered sample.

A further argument is that the position of the Ru-1212 peaks is not fixed for all samples and seems to follow the temperature, at which intergranular coupling is established. In another case, where the Ru-1212 magnetization peaks have been observed Klamut1 , the sample had a higher Tc of 35 K compared to ours and the peak was observed above 25 K. In this case it would be very difficult to attribute the observed peak to Sr-2116 impurities, not only quantitatively, like in our case, but also as far as the peak temperature is concerned.

The above analysis indicates, that the magnetization peaks observed in the superconducting state of Ru-1212 are related to the superconductivity of this compound. In the following we will show though, that they are not an intrinsic property of this compound, but arise from the movement of the sample in a non-homogeneous field during the measurement with the SQUID magnetometer. Nevertheless, we begin by discussing a model for the explanation of these peaks, as if they represented an intrinsic property of the compound. This discussion will (i) help us illustrate clearly the danger of developing impressive, but invalid, explanations, when a careful check of the SQUID magnetization of Ru-1212 has not been done and (ii) serve as the starting point for the proposal and evaluation of several tests by which the validity of the magnetization features calculated by the SQUID’s software for Ru-1212 (or any other superconductor) can be investigated.

### III.3 A possible (but not real) origin of the Ru-1212 magnetization peaks

Recently, the occurrence of the Paramagnetic Meissner Effect (PME) has been predicted for superconductors, when they are cooled in a field below Tc, from the self-consistent solution of the Ginzburg-Landau equations Zharkov . The physical picture behind this model is as follows Zharkov : when a vortex is present inside a superconductor, the current around it flows in a direction to screen the vortex field from entering the bulk of the sample. In a magnetic field, additional surface current flows in order to prevent the field from entering the interior of the superconductor. These two currents flow in opposite directions and contribute with different signs to the superconductor’s magnetization M. The current around the vortices gives a positive (paramagnetic) contribution, while the surface current gives a negative (diamagnetic) contribution. The resulting value of M can be negative or positive depending on the value of the magnetic field. The PME arises then, from the imbalance between the two screening currents. This physical picture can explain the magnetization peaks observed for our Ru-1212 samples as the result of the competition between the screening currents around the vortices, which dominates at temperatures close to Tc, and the surface current, the diamagnetic contribution of which starts to dominate at lower temperatures.

The model predicts the existence of vortex states with different vorticities, each of which exists in a certain range of magnetic fields. Some of these states are paramagnetic and some diamagnetic. Equilibrium transitions between them do not allow the observation of the PME. On the other hand, if metastable states exist, introduced by vortex pinning, the observation of the PME is possible. In order to investigate this feature of the model, we did f.c. d.c. magnetization measurements using different cooling rates. The result is shown in figure 5. The slow cooling measurement, which showed the peak, was done by cooling the sample from 200 K with a cooling rate of about 0.2 K/min below 40 K. The cooling rate was controlled by taking the measurements during cooldown (similar to the procedure followed for the curves of figure 3) with a step of 0.2 K from 40 to 7 K. The curve was remeasured during warm up and no hysteresis was observed. The fast cooling measurement was done by cooling the sample directly from 200 K to 7 K within 2 hours. The measurements were taken during warm up. The difference between the two curves is obvious below the peak position of the slow cooling measurement. The fast cooling measurement was repeated under the same cooling conditions. Now the measurements were not taken immediately after reaching 7 K, but after the sample was left at 7 K for 24 hours. This second measurement, as shown in figure 5, was identical with the first one under fast cooling conditions. After this second fast cooling measurement, the slow cooling measurement was also repeated and it gave the same result as the first slow cooling measurement. The observed dependence of the measured magnetization on the cooling rate is in accordance with the model’s prediction, that the observation of the PME is a signal of metastability. At this point we should note, that considerations similar to those developed here were recently used to introduce the PME in MgB2 Horvat . There the peak position, where the curves measured under different cooling rates merge, was identified as the irreversibility temperature connected with the vortex pinning that introduces metastability.

According to Zharkov Zharkov , the appearance of the PME is determined by the size parameter A = (R/$`\kappa `$)(2$`\pi `$H/$`\mathrm{\Phi }`$0)1/2, where R is the diameter of the sample, $`\kappa `$ is the Ginzburg-Landau parameter, H the magnetic field and $`\mathrm{\Phi }`$0 the flux quantum. For A = 1, for example, no PME is expected Zharkov , while for A = 3 the appearance of the PME is allowed Zharkov . The dependence of the PME appearance on the parameter A can explain why intergranular coupling has to be established, before the PME is observed. First of all, for samples with grain size of the order of the penetration depth or smaller, the establishment of intergranular coupling is the only possibility for the creation of the surface current, which creates the diamagnetic contribution to M. On the other hand, for samples with grain size bigger than the penetration depth, if this size gives a value of A not consistent with the appearance of the PME, then the effect will not be observed before intergranular coupling is established. So, intergranular coupling changes the characteristic size of the sample and can lead from A values not consistent with the appearance of the PME to values consistent with it.

In the study of MgB2, Horvat et al. Horvat  recognize that the appearance of the PME in the z.f.c. data is difficult to understand. They consider this a feature, which distinguishes the PME reported for MgB2 from the PME in the conventional or high temperature superconductors. For Ru-1212 the appearance of the PME in the z.f.c. curve (see z.f.c. data in figure 2) can be understood if one keeps in mind, that Ru-1212 is a magnetic superconductor and even when it is cooled in zero magnetic field, it will react to its own magnetism. An indication for this is given by the measurement in “0” field presented in figure 3, although the existence of a tiny remanent field can not be avoided. Since within the framework of the model presented a vortex state is necessary for the observation of the PME, the observation of the magnetization peak in this curve also can be considered indicative of the existence of the spontaneous vortex phase in Ru-1212, as has been already discussed for the Ruthenium-cuprates Bernhard1 ; Sonin .

### III.4 The real origin of the Ru-1212 magnetization peaks

In section III.3 we proposed a model for the explanation of the d.c. magnetization measurements on our Ru-1212 sample, which practically explains all the experimental observations. Within this model, the observed features in the magnetization of our Ru-1212 sample were explained as arising from the competition of a paramagnetic contribution from the currents around the vortices and a diamagnetic contribution from the surface current. If this is the case, we expect that a reversal of the field should lead to a reversal of the observed features. In figure 6, we show the slow cooling measurement of figure 5 in a field of -1 mT. While the paramagnetic signal observed above 30 K is reversed as expected, the peak is observed again but it has not been reversed by the inversion of the field. This fact indicates, that the mechanism proposed in section III.3 for the explanation of the magnetization peaks observed in the superconducting state of Ru-1212 is not the appropriate one.

In order to further investigate the validity of our assumptions in section III.3, we have tested the reproducibility of our measurements after the superconducting magnet of the magnetometer was cycled in the following way: 0 T $``$ 6 T $``$ -6 T $``$ 0 T $``$ 0.05 mT. The f.c. measurement after this cycle is shown in figure 7. It is obvious that the effect has reversed sign compared to figure 2. Now a decrease of the magnetization is observed below Tc followed by a rapid increase of the magnetization at lower temperatures.

The result presented in figure 6 is similar to an observation made by Blunt et al. Blunt , when they investigated the origin of “paramagnetic” moments in the superconducting state of (Tl0.5V0.5)Sr2(Ca0.8Y0.2)Cu2Oy. On the other hand, the result of figure 7 is reminiscent of effects reported by McElfresh et al. McElfresh  for an YBCO thin film, where field profiles symmetric with respect to a set value of the magnetic field created magnetization features with reversed signs in the superconducting state of the sample. We note, that the cycling of the magnet to high fields, before the measurement of figure 7, is very likely to have changed the profile of the field compared to that of measurements presented in previous figures McElfresh .

In both cases reported above, the authors Blunt ; McElfresh  have interpreted their observations as artefacts arising from the movement of the sample in a non-homogeneous field during the measurement with the SQUID magnetometer. The problem is as follows: For many of the commercially available magnetometers the measurement requires the motion of the sample through a pickup coil system. These coils are wound in a second derivative configuration, where the two outer detection loops, located at a distance A from the center of the magnetometer’s magnet, are wound oppositely to the two central loops located at the center of the magnet. During the measurement, the movement of the sample through the pickup coils induces currents in the detection loops, which, through an inductance L, create magnetic flux in the SQUID circuit, resulting in an output voltage V, which depends on the position of the sample z. This signal V(z) is fitted by the SQUID’s software for the determination of the sample’s magnetic moment. Nearly all analysis methods of the V(z) signal make two significant assumptions for the magnetic moment of the sample: (a) that it is approximated by a magnetic dipole moment and (b) that the sign and value of this moment do not change during the measurement. A superconducting sample though, will follow a minor hysteresis loop during the measurement, when the magnetometer’s field is not homogeneous. Libbrecht et al. Libbrecht , using the Bean model Bean ,have shown that, depending on the sample properties and the level of field inhomogeneity, it is even possible, that the sample’s magnetization will change sign and eventually reach its original value with reversed sign at the end of the scan in a non-homogeneous field. Such problems creating spurious signals in the d.c. magnetization of superconducting materials have been discussed in the past by several authors McElfresh ; Blunt ; Libbrecht ; Schilling ; Braunisch .

The above analysis motivated us to investigate whether Ru-1212, in its superconducting state, shows a similar sensitivity to field inhomogenieties, which could create artefacts in its measured magnetization. We worked in the following way: another cycle of the magnet from high magnetic fields to zero and finally to 0.25 mT was done. After this cycle the peak in the f.c. d.c. magnetization data reappeared, as shown in figure 8a. After this measurement and without changing the field, we placed the sample in the center of the pickup coil system and recorded the output voltage of the SQUID circuit as the sample was cooled from 200 K without moving it. With this type of measurements absolute values of the magnetization can not be calculated, however, the recorded signal is proportional to the magnetization of the sample. The result is shown in figure 8b. No peak like feature is observed at low temperatures in this measurement. Only a decrease of the magnetization indicative of field expulsion as the sample is entering the superconducting state is observed. In the same figure we have also included the z.f.c. measurement for our sample. Again, no peak like feature of the magnetization at low temperatures is observed. The measurements presented in figure 8 clearly illustrate that the peak like features of the d.c. magnetization observed in the superconducting state of Ru-1212 are an experimental artefact arising from the movement of the sample in an inhomogeneous field during the measurement in the SQUID magnetometer.

In view of the observed sensitivity of the Ru-1212 measured magnetization to field inhomogenieties and since we have no evidence that a field reversal, similar to that for the measurements presented in figure 6, or cycling of the magnet, similar to that before the measurements presented in figure 7, affect the field profile of the superconducting magnet in a systematic way, we consider measurements similar to those in figure 8b as the most reliable test, that helps to decide, whether the observed features in a SQUID magnetization measurement of Ru-1212 (or any other superconductor) represent a true property of the compound or not.

### III.5 Some remarks for Sr-2116

The field profile of the SQUID’s superconducting magnet can affect the measured magnetization not only of superconducting samples (like Ru-1212) but also of any sample showing hysteresis in its magnetization. This sets the validity of the reported magnetization peak for Sr-2116 under question (see section III.2 and reference ). Thus, we tested Sr-2116 as introduced above. In figure 9a we show a f.c. measurement of a Sr-2116 sample in a negative field of -0.25 mT and in figure 9b a f.c. measurement of the SQUID setup’s output voltage in a field of 0.25 mT. The peak, which has been attributed to a response of the paramagnetic Gd moments to the antiferromagnetic ordering of the Ru moments at about 35 K Papageorgiou , is reversed in the negative field and is also obvious in in the measurement without moving the sample. These measurements show, that the reported Papageorgiou  magnetization peak for Sr-2116 represents a true property of the material.

## IV Concluding remarks

In summary, we have investigated the origin of “paramagnetic”-like features (see figures 2 and 7) in the superconducting state of Ru-1212. We have shown, that these features, with high probability, are experimental artefacts arising from the movement of the sample in an inhomogeneous field during the measurement with the SQUID magnetometer. In view of the observed sensitivity of the Ru-1212 measured properties to the field profile of the superconducting magnet, we have proposed and evaluated several tests, which can help to decide whether the observed features in a SQUID magnetization measurement of Ru-1212 is an intrinsic property of the compound or not, with the most reliable one being the recording of the SQUID circuit’s output voltage as the sample is cooled or warmed up in the magnetometer without being moved. We consider these tests as general tests, which can be used for the evaluation of the data on any superconducting sample.

Our work shows, that any “paramagnetic”-like features in the superconducting state of Ru-1212, which could easily be related to some response of the Gd moments in this compound and considered as an indication for the lack of a Meissner state for Ru-1212, have to be evaluated carefully. On the other hand, features indicative of the existence of the Meissner state for this compound have also to be investigated carefully. Our work together with the measurements of McElfresh et al. McElfresh  indicate, that any measured “paramagnetic”-like features can easily be turned to “diamagnetic”-like features, which could be mistaken as an indication of the existence of a bulk Meissner state for Ru-1212, by a reversal of the field profile with respect to the set value of the magnetic field. The f.c. measurement on a stationary sample presented in figure 8b indicates, that the Meissner state indeed exists for Ru-1212. Nevertheless, similar measurements, where the calculation of the absolute values of the magnetization will be possible for an estimation of the superconducting volume of the sample, are necessary, in order to clarify this issue.

Both here and in our previous work Papageorgiou  we have shown, that Sr-2116 can also be a good candidate for the explanation of any “peculiar” features in the low temperature properties of Ru-1212 like d.c. magnetization and specific heat. Since new Ru-1212 compounds with other lanthanides in the place of Gd have recently been reported Williams ; Takagiwa ; Hai ; Ruiz , we note, that there is a whole series of Sr-2116 compounds also with other lanthanides in the place of Gd, which are magnetic at low temperatures Battle1 ; Battle2 ; Battle3 ; Battle4 ; Battle5 ; Doi . Some of these Sr-2116 compounds doped with Cu, like Sr2YRu1-xCuxO6 (but not Sr2GdRu1-xCuxO6 Papageorgiou ) are also reported superconducting with a Tc similar to those of the Ru-1212 compounds Wu1 ; Chen2 ; Wu2 ; Blackstead ; Wu3 . Careful studies, similar to those in our previous work Papageorgiou  and in section III.2 are necessary to exclude the possibility, that trace impurities of Sr-2116 compounds are responsible for the properties attributed to the Ru-1212 phase.

###### Acknowledgements.

We would like to thank Dr. Alexander Schindler for useful discussions.


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# Magnetization anomalies in the superconducting state of RuSr2GdCu2O8 and the magnetic study of Sr2GdRuO6

## 1 Introduction

The discovery of coexistence of superconductivity and weak ferromagnetism in RuSr2GdCu2O8 (Ru-1212)  has triggered a large number of studies of the properties of this material. From all these studies it becomes obvious, that the preparation method plays a very important role, in particular as far as the superconducting properties of the compound are concerned. For example, there are reports of non-superconducting samples of Ru-1212  as well as for samples, which exhibit bulk superconductivity . A key compound for the preparation of Ru-1212 is Sr2GdRuO6 (Sr-2116), either as an intermediate product during the preparation of Ru-1212 , or used directly as a precursor . The (nominal) valency of Ru in Sr-2116 (Ru5+) minimizes the likelihood of formation of the itinerant ferromagnet SrRuO3 during the preparation of Ru-1212 in the two-step process .

Sr2GdRuO6 belongs to the class of double perovskites of the general chemical formula A2BB$`^{^{}}`$O6 (often called “2116” compounds because of their stoichiometry) with A=Ca, Sr, Ba, B=Y, La, Nd, Eu, Gd-Lu and B$`^{^{}}`$=Ru. Their structure, as determined by neutron  and X-ray diffraction , is that of a distorted perovskite with monoclinic space group P21/n and can be visualized as corner-sharing tilted oxygen octahedra alternately centered by B and B$`^{^{}}`$, while the bigger A ions are located in the area between the oxygen octahedra.

These compounds offer the rare opportunity to study the magnetic behavior of a 4d3 electron system. Indeed, magnetic ordering of highly oxidized cations from the second transition series is quite unusual but Battle et al.  have shown, that the Ru5+ ions in these compounds order antiferromagnetically at low temperatures.

A particular interest for a more detailed investigation of the magnetic properties of Sr2GdRuO6 arises from the fact mentioned above, that this compound is involved in the preparation methods of the magnetic superconductor Ru-1212. In this work we investigate samples of Ru-1212 prepared using Sr-2116 as a precursor material and examine the origin of distinct peaklike anomalies in the d.c. magnetization curves of Ru-1212 upon entering the superconducting state. We conclude, that these peaks cannot be explained in terms of some of our precursor material remaining as an impurity phase in the superconducting samples. A tentative explanation of the origin of the peaks, based on the interpretation of our data on Sr-2116, is given.

## 2 Experimental

Polycrystalline samples of Ru-1212 were prepared following a two-step procedure. First, Sr-2116 was prepared from stoichiometric quantities of RuO2, Gd2O3 and SrCO3. The powders were mixed, calcined at 950 C in air, pressed into pellets and fired for 16 h at 1250 C in air. In a second step, the obtained Sr-2116 was mixed with CuO, pressed into pellets and fired for 120 h at 1060 C in flowing oxygen.

Resistance measurements were performed by a standard four-probe a.c. technique (at 22.2 Hz) on bar-shaped pieces cut from the pellets using silver paint contacts. a.c. susceptibility measurements were done with a home-made susceptometer using a standard lock-in technique at different field amplitudes.

d.c. magnetization measurements were done with a commercial SQUID magnetometer (Cryogenic Consultants Ltd. S-600), which allows measurements in the temperature range 1.6 K $``$ T $``$ 300 K in magnetic fields up to 6 T. For the low field measurements, a paramagnetic AuCr sample was used as a standard for the determination of the remanent fields in the magnet. An external current source (Knick DC-Current-Calibrator J152) was used to cancel the remanent and earth fields and apply the appropriate current, so that the desired field could be achieved.

The Ru-1212 piece studied in the magnetometer was powdered afterwards and the x-ray powder diffraction pattern was taken on a Philips X-pert diffractometer with primary beam Ge(111) Johanson monochromator using Cu K$`\alpha `$1 radiation. Flat plate geometry was used with the sample sieved on vacuum grease on a low background quartz sample holder. The result shown in figure 1a indicates, that within the resolution of the instrument the sample is single phase with the impurity phases (if any) representing less than 3 % of the sample. The tetragonal lattice parameters (spacegroup P4/mmm) are $`a=3.837(4)\AA ,c=11.56(1)\AA `$.

A similar X-ray scan was done for the Sr-2116 sample studied in the magnetometer with a Seifert XRD 3000 P diffractometer and revealed, that traces of the original Gd2O3 powder were still present in the sample. The room temperature lattice parameters for our Sr-2116 sample were (spacegroup P21/n) $`a=5.808(5)\AA ,b=5.819(5)\AA ,c=8.212(8)\AA ,\beta =90.3(1)^{}`$.

X-ray powder diffraction data of a similarly prepared Sr-2116 sample at low temperatures were collected in transmission geometry at the high energy beamline ID15B of the European Synchrotron Radiation Facility (ESRF). X-rays of energy 90 keV were selected by a bent Si (511) monochromator, which focuses the beam in the horizontal plane . The size of the beam was adjusted to several mm height and a width of 0.5 mm. A MAR 345 image plate reader was used as detector at a distance of approx. 730 mm from the sample. The wavelength was determined to 0.14668 Å from a NBS-676 LaB6 standard. The sample was contained in a 0.7 mm lithiumborate glass (glass No. 50) capillary and was rocked several degrees during the measurement in order to improve randomization of the crystallites. Data were taken at several temperatures down to 23 K. Data reduction was performed using the program FIT2D , resulting in diagrams of corrected intensities versus the scattering angle 2$`\theta `$. It was observed, that the diffracted intensity was quite uniformly distributed over the Debye-Scherrer rings, ruling out severe grain size effects and preferred orientation. Low angle diffraction peaks had a FWHM of 0.04 2$`\theta `$, which can be considered the highest resolution for this particular setup. At this high energy, no corrections for absorption are necessary. The data presented in the lower part of figure 1b show, that the crystal structure of the compound is stable at least down to 23 K.

## 3 Results and Discussion

### 3.1 Superconductivity and magnetism of RuSr2GdCu2O8

In figure 2 our resistivity and a.c. susceptibility results on Ru-1212 are shown.

The resistivity measurements (inset) reveal a metallic behavior of the sample at high temperatures with a small cusp at about 135 K related to the magnetic transition, which occurs at this temperature (see d.c. magnetization measurements presented below). At lower temperatures a slight upturn of the resistance is observed above the onset of superconductivity at 50 K, while the resistivity becomes zero at 30 K. At this temperature, the inter-granular coupling is established and a clear diamagnetic response is observed in the real part of the a.c. susceptibility with the corresponding loss peaks in the imaginary part. Typical for shielding due to inter-granular coupling, the transition widens and shifts to lower temperatures as the a.c. field amplitude is increased.

The results of d.c. magnetization measurements for three different measuring fields are shown in figure 3.

At about 135 K, a magnetic transition is observed for the compound. The exact temperature of this transition depends on the applied field and decreases slightly from 137 K at 0.25 mT to 134 K at 10 mT. Although it was originally believed, that this transition is due to ferromagnetic ordering of the Ru moments, powder neutron diffraction studies  revealed an antiferromagnetically ordered state of the Ru moments and put a limit of about 0.1 $`\mu _B`$ per Ru on any ferromagnetic component. The presence of a ferromagnetic component is indicated by hysteresis loops in M-H curves measured in the magnetically ordered state . For these results to be consistent with the neutron diffraction data, the antiferromagnetically ordered Ru moments must be canted to give a net magnetic moment. This canting is thought to be associated with rotations of the RuO6-octahedra . The zero field cooled (z.f.c.)-field cooled (f.c.) hysteresis observed for our M-T curves in the magnetically ordered state presumably arises  from an increased canting of the Ru moments due to the presence of the external magnetic field in the f.c. process, which leads to higher values of the magnetization compared to the z.f.c. branch. The z.f.c.–f.c. hysteresis above about 30 K is also reminiscent of spin glass behavior and could involve freezing out of the canted component below the irreversibility temperature, which would be defined by the point, where the z.f.c. and f.c. curves merge.

In figure 3a, distinct anomalies of the magnetization are observed upon entering the superconducting state. The magnetization shows a clear increase at 25 K and reaches a peak at 15 K. In a low field (0.25 mT), the magnetization decreases below 15 K because of the field expulsion due to superconductivity. While the flux expulsion does not saturate down to our lowest measuring temperature, probably due to the small grain size ($`\mu \text{m}`$) or possibly due to undetected sample imhomogeneity, it should be noted, that the signal corresponds to a complete flux expulsion from 25% of the sample volume. At 1 mT this peak is still observed but its height has decreased and at 10 mT no peak is present (although the curves show a cusp at low temperatures) and the flux expulsion characteristic of a superconductor entering the Meissner state has disappeared. Similar anomalies have also been observed by Klamut et al. . Their sample had a slightly higher superconducting transition temperature of 35 K and the peak of the magnetization was observed at a higher temperature, above 25 K. In  two proposals were made, without further analysis, for the interpretation of the observed anomaly in the d.c. magnetization curve: (a) in terms of a change of the magnetic ordering of the Ru moments upon entering the superconducting state and (b) in terms of an anomalous flux lattice behavior. It appears noteworthy, that such magnetization features have not been observed in all studies of superconducting Ru-1212 . In our case, we take into account the information, that Ru moments order antiferromagnetically in 2116 compounds  and the fact, that we used Sr-2116 as a precursor material for the preparation of Ru-1212. Thus, we decided to investigate the possibility, that the anomalies are due to Sr-2116 impurities, which could have been present in our Ru-1212 samples as a second phase in an amount $``$ 3 %, in accordance with our X-ray results.

### 3.2 Magnetic study of Sr2GdRuO6

The samples of Sr-2116 were prepared as described above at the first step of the preparation of Ru-1212. Figure 4 shows the z.f.c. and f.c. magnetization taken in a field of 0.25 mT.

The curves consist of a high temperature paramagnetic regime, where, as expected, the magnetization is a linear function of the magnetic field (c.f. figure 6b). At lower temperatures, a small anomaly of the magnetization is observed between 35 K and 30 K. The position of this cusp-like feature is marked by an arrow in figure 4 and in figure 5, where it is more clearly visible. From our low temperature structure data (figure 1b) we can exclude the possibility, that this slight cusp is related to a structural transition. Below 30 K, the magnetization begins to increase rapidly and reaches a peak at 18 K. A second peak of the magnetization is observed below 3 K, as shown in the inset of figure 4.

The temperature at which this second peak is observed is similar to the antiferromagnetic ordering temperature of the Gd moments in Ru-1212, as determined by neutron diffraction  and d.c. magnetization studies . In order to exclude the possibility, that this second peak at 3 K or the cusp above 30 K are due to the trace impurities of cubic Gd2O3 present in the Sr-2116 sample, we also studied the magnetic properties of the Gd2O3 powder used for sample synthesis (Chempur 99.99 % pure). No transition was observed down to the lowest temperature investigated (1.6 K) in accordance with the report by Moon and Koehler .

Figure 5 shows, that the position of the cusp-like anomaly between 35 K and 30 K as well as that of the increase of the magnetization at 30 K are rather independent of magnetic field, while the position of the peak slightly shifts from 18 K at 0.25 mT down to 14 K at 35 mT and the magnetization decrease below the peak temperature becomes less pronounced.

At 50 mT, the peak has disappeared and a ferromagnetic-like curve is observed. A f.c. magnetization curve taken at 200 mT (not shown) between 7 K and 300 K appears paramagnetic-like throughout the whole temperature range but the cusp in the 35-30 K temperature range is again clearly visible.

The hysteresis between the z.f.c. and f.c. curves (figure 4) is reminiscent of that observed for Ru-1212 and indicates, that Sr-2116 is not a simple antiferromagnet. As proposed for Ru-1212, such a behavior could be caused by a canted arrangement of the spins giving rise to a net magnetic moment. The presence of a ferromagnetic component is indicated by the hysteresis loop obtained at 16 K, which is shown in figure 6a. Using the remanent magnetization as a measure of the spontaneous ferromagnetic moment this is $`0.03\mu _B`$ per formula unit. We should note, that for the measurement in figure 6a the field was changed between 6 and -6 T. For clarity only the low field part of the measurement is presented.

A possible scenario for the explanation of these observations is the following: At about 35 K the expected  antiferromagnetic ordering of the Ru moments takes place. Presumably, this corresponds to the 31 K ordering temperature of the Ru moments in Sr-2116 reported in literature . A canting of the Ru moments creates an internal field, which at about 30 K polarizes the Gd moments leading to the observed rapid increase of the magnetization shown in figure 4. At about 18 K, Gd-Gd antiferromagnetic interactions start to dominate over this polarizing effect and the magnetization decreases. The ordering of the Gd moments takes place at about 3 K.

This interpretation of the data is consistent with a scenario proposed in  in order to explain the magnetic properties of Gd2CuO4, where Cu orders antiferromagnetically at 260 K. Here, the canting of the Cu moments polarizes the Gd moments at about 100 K. Below 20 K, Gd-Gd interactions begin to dominate, while the actual antiferromagnetic ordering of the Gd moments, as indicated by specific heat and magnetization measurements, occurs at 6.5 K. In an applied magnetic field, the peak at 20 K is shifted to lower temperatures, similar to our results on Sr-2116 presented in figure 5, and finally merges with the one at 6.5 K, which is associated to the antiferromagnetic ordering of the Gd moments.

In a study of a series of Cu-doped 2116 compounds  superconductivity was observed, which appears to coexist with antiferromagnetic order of Ru5+ ions. A sharp increase of the susceptibility at 30 K similar to that in figure 4 was interpreted as the signature of ferromagnetic ordering due to double exchange between Ru ions of different valencies . Double exchange was introduced by Zener  and in recent years represents a standard approach for the explanation of the transport and magnetic properties of the colossal magnetoresistance manganites, such as La1-xSrxMnO3. There, the transfer of electrons through an oxygen ion between Mn ions of different valencies, namely 3+ and 4+, created through partial substitution of the trivalent La by divalent Sr, gives rise to a ferromagnetic coupling between these ions. In the 2116 compounds it was proposed, that partial doping with Cu, likely to be in the 3+ state, promotes the formation of Ru6+ ions. The double exchange mechanism would then involve Ru5+ and Ru6+ ions.

In the case of Sr-2116 studied here, it is difficult to visualize the origin of double exchange since no Cu doping is involved. On the other hand, Donohue and McCann , who prepared Sr-2116 compounds in a way similar to ours, report, that their sample was oxygen deficient with a composition of Sr2GdRuO5.95. Such a deficiency on the oxygen site could create Ru ions of different valencies and give rise to double exchange. Oxygen uptake during a heat treatment in oxygen atmosphere is then expected to affect the magnetic properties of such samples.

Following these ideas, we have treated the Sr-2116 sample used for the magnetization measurements presented in figures 4-6 for 5 days at 1060 C in flowing oxygen. This treatment equals the second step in the preparation of Ru-1212 as described above (section 2). In figure 7 a pair of M-T curves is shown, which were taken after the oxygen treatment.

It is obvious, that although all the features of the curves described so far are retained and the f.c. curve remains almost unchanged, the height of the z.f.c. peak is significantly reduced. Incorporation of oxygen to the sample would lead to a change of the valency of Ru ions towards the expected one of 5+. This would then suppress double exchange. A change of the valency of some Ru ions after the oxygen treatment would also change the Ru-Gd interactions in the sample. This could explain why the peak shown in the inset of figure 4, tentatively associated with Gd-moment ordering, appears now (figure 7) to be shifted to a lower temperature $`1.6\text{K}`$. The interaction of the Ru and Gd sublattices in Ru-1212 was recently discussed in .

On the basis of the above interpretation, the peak at 18 K must be related to the antiferromagnetic ordering of the Ru5+ moments. This is inconsistent with the reported  transition temperature. Within this scenario, the origin of the cusp in the magnetization curve between 30 and 35 K is unclear. It must also be mentioned, that the suppression of the z.f.c. magnetization seen in figure 7 could be related to a change in the morphology of the sample due to the long annealing times in flowing oxygen. In Ru-1212  for example, the ratio of the domains with opposite sense of RuO6-octahedra rotation is assumed to depend on the annealing of the sample.

### 3.3 Comparison between RuSr2GdCu2O8 and Sr2GdRuO6

In view of the results presented so far it is very tempting to interpret the anomalies of the d.c. magnetization of Ru-1212 upon entering the superconducting state in terms of Sr-2116 impurities in the sample. The magnetization of Sr-2116 is similar to that of the anomalies of Ru-1212 and the temperatures of the magnetization peak observed for the two compounds differ only by about 3 K. A quantitative comparison can be done based on the mass susceptibilities or the magnetization per gram of the sample used for the measurements presented in figure 3, which may be supposed to be of unknown composition. The z.f.c. moment of Sr-2116 measured in a field of 0.25 mT (figure 4) is about $`1.7\times 10^3\mu _B/\text{(f.u. Sr-2116)}1.72\times 10^5\text{Am}^2/\text{g}`$, while the peak increase above the z.f.c. “plateau” in the sample of figure 3a reaches $`3.6\times 10^3\mu _B/\text{(f.u. Ru-1212)}2.9\times 10^5\text{Am}^2/\text{g}`$. In order to explain the z.f.c. anomaly observed in this sample in terms of Sr-2116 impurities one would thus need a mass of the impurity, which would correspond to 2.9/1.72 times the sample mass, which, of course, is impossible. Different estimates are reached, if a stronger moment of the Sr-2116 impurity is assumed, as detailed below.

On the basis of the assumption, that double exchange is causing the rapid increase of the magnetization for Sr-2116 at 30 K one might argue, that possible Sr-2116 impurities in the Ru-1212 sample have higher oxygen deficiencies than the sample of figure 4, which would give rise to more pronounced magnetization peaks without requiring large amounts of Sr-2116 impurities. One should keep in mind though, that possible impurities underwent an oxygen treatment during the last step of the preparation of Ru-1212. According to the result presented in figure 7 this would suppress double exchange.

Other impurities, that could be responsible for the observed magnetization peaks in the Ru-1212 sample are Ru-deficient Sr-2116 or Cu-doped Sr-2116. Such samples were also prepared and investigated with the result shown in figure 8.

The sample of Sr2GdRu0.9O6 was prepared in a way similar to the Sr2GdRuO6 sample. In order to simulate the most likely way of formation of Cu-doped Sr2GdRu0.9Cu0.1O6 impurities in Ru-1212, a Sr2GdRu0.9O6 sample was used as a precursor to which CuO was added. The pelletized mixture was heated at 1060 C for 120 h in flowing oxygen. A comparison of the X-ray powder patterns of these samples (done on the Seifert diffractometer) with that of a Sr-2116 sample is shown in figure 1b. Although unidentified impurity peaks were present (together with Gd2O3 trace impurities for Sr2GdRu0.9Cu0.1O6), we decided to investigate these samples. The idea is, that, within the framework of double exchange for example, Ru deficiencies or Cu doping could enhance the magnetism of these compounds compared to that of Sr-2116. Indeed, as shown in figure 8 the magnetization of these compounds is enhanced with peaks at about 20 K, while no low temperature peak was observed in the f.c. curves, which could be associated to Gd ordering in these compounds. A quantitative analysis of the results, similar to the one above for Sr-2116, using a moment of $`46\times 10^3\mu _B/\text{f.u.}`$ (figure 8) leads to similar result, that a large fraction of the sample (50-70%) would have to consist of the impurity phase. Given the single-phase nature of the x-ray powder pattern, which was taken on the sample used for the magnetic measurements presented in figure 3, this is impossible.

For the Sr2GdRu0.9Cu0.1O6 sample no indication of superconductivity was observed in our d.c. magnetization measurements unlike the report for other Cu doped 2116 compounds . It must be mentioned, however, that these superconducting samples were prepared at a much higher temperature of about 1400 C and that a similar sample with Ba in the place of Sr, although it was prepared at high temperatures, did not show superconductivity .

## 4 Concluding remarks

In summary, we have observed distinct anomalies in the d.c. magnetization curves of Ru-1212 upon entering the superconducting state. In order to determine whether these anomalies could be due to Sr-2116 impurities in the sample, an extensive study of the magnetic properties of Sr-2116 in terms of d.c. magnetization measurements was carried out. The magnetic properties of Sr-2116 are described according to the following scenario: At $``$35 K the Ru moments order antiferromagnetically but in a canted arrangement. This canting of the Ru moments creates an internal field, which polarizes the Gd moments, leading to a rapid increase of the magnetization at about 30 K. At $``$18 K, Gd-Gd antiferromagnetic interactions start to dominate the polarizing effect and the magnetization decreases. The actual antiferromagnetic ordering of Gd takes place at about 3 K. An alternative (less likely) scenario for the explanation of the data based on double exchange between Ru ions of different valencies was also presented.

In addition to (nominally) stoichiometric Sr-2116, the magnetization of Ru-deficient and Cu-doped Sr-2116 compounds was also measured; no indication for superconductivity of the Cu doped Sr-2116 compound was found in d.c. magnetization measurements.

Although similarities were observed in the magnetic behavior of Sr-2116 and the magnetization peaks of the Ru-1212 sample, a direct quantitative comparison clearly revealed, that very large amounts of Sr-2116 (or the related compounds studied), easily detected by X-ray powder diffraction, would be required for the explanation of the magnetization peaks in terms of impurities present in the sample. Since no such amounts were observed, the peaks are rather an intrinsic property of Ru-1212. The proposals of Klamut et al.  for the explanation of this property were mentioned above in section 3.1. The fact, that from our data and the data presented in , the onset of the peaks occurs at the temperature where inter-granular coupling is established indicates, that the effect is related to superconductivity. An alternative explanation based on the scenario presented above for the magnetic behavior of Sr-2116 is the following: In Ru-1212, the Ru moments order antiferromagnetically at $``$135 K in a canted arrangement, which creates an internal field, that in turn polarizes the Gd moments at low temperatures ($``$25 K). Below 25 K, a combination of the polarizing effect, the Gd-Gd antiferromagnetic interactions and the effect of superconductivity leads to the observation of the peak-like feature. In any case, an open question is why this low temperature peak in the magnetization curve of Ru-1212 is not observed  in all d.c. magnetization studies of Ru-1212. A more detailed investigation of the magnetic properties of Ru-1212 samples similar to that presented in section 3.1 of this paper, which could provide an answer to this question and clarify the origin of the observed peaks, is now in progress and details will be published in the near future.

## 5 Acknowledgments

We thank Wolfgang Ettig and Armin Dertinger for their valuable technical support and help.


text:
# Comparison of hadronic rescattering calculations of elliptic flow and HBT with measurements from RHIC

## I Introduction

Results of the Year-1 running of the Relativistic Heavy Ion Collider (RHIC) for Au+Au collisions at $`\sqrt{s}=130`$ GeV have shown suprisingly large pion elliptic flow Adler:2001a  and suprisingly small radii from two-pion Hanbury-Brown-Twiss interferometry (HBT) Adler:2001b ; Adcox:2002a . Attempts to explain both results in a consistant picture have so far been unsuccessful. Hydrodynamical models agree with the large elliptic flow seen in the RHIC data Kolb:1999a  but significantly disagree with the experimental HBT radii Rischke:1996a . On the other hand, relativistic quantum molecular dynamics calculations which include hadronic rescattering, for example RQMD v2.4 Sorge:1989a , significantly underpredict the elliptic flow seen in the RHIC data Sorge:1995a  but predict pion HBT radii comparable to the data Hardtke:1999a . A calculation has recently been made to extract HBT radii with a hydrodynamical model coupled with a hadronic rescattering afterburner with the result that the HBT radii are significanly larger than measurements Soff:2000a . This lack of a single model to explain both results has been our first big mystery from RHIC. It has been suggested that we should call into question our current understanding of what information pion HBT measurements give us Gyulassy:2001a .

In an effort to address this mystery, the present work explores a somewhat different picture of the nuclear collision than those presented above. In this picture, hadronization into a simple thermal-like state occurs soon (about 1 fm/c) after the initial collision of the nuclei followed by hadronic rescattering until freezeout. The goal will thus be to test whether hadronic rescattering alone can generate enough general flow in the system to explain both the elliptic flow and HBT results from RHIC starting from a simple non-flowing initial state. Note that this approach, while similar to the relativistic quantum molecular dynamics calculations mentioned above, differs from them in the choice of the model of the initial state of the system before hadronic rescattering commences (e.g. the other models use a color string picture for the initial state) Sorge:1989a . The simple initial state model used here is meant to be a construction to parameterize the true initial state with a few parameters which can be adjusted to help the rescattering calculation agree with the RHIC results. If it is possible to obtain reasonable agreement with the data, then one might ask how early in the calculation one can go and still maintain a physically motivated model. The discussion of this important point is deferred until later.

## II Calculational Method

A brief description of the rescattering model calculational method is given below. The method used is similar to that used in previous calculations for lower CERN Super Proton Synchrotron (SPS) energies Humanic:1998a . Rescattering is simulated with a semi-classical Monte Carlo calculation which assumes strong binary collisions between hadrons. The Monte Carlo calculation is carried out in three stages: 1) initialization and hadronization, 2) rescattering and freeze out, and 3) calculation of experimental observables. Relativistic kinematics is used throughout. All calculations are made to simulate RHIC-energy Au+Au collisions in order to compare with the results of the Year-1 RHIC data.

The hadronization model employs simple parameterizations to describe the initial momenta and space-time of the hadrons similar to that used by Herrmann and Bertsch Herrmann:1995a . The initial momenta are assumed to follow a thermal transverse (perpendicular to the beam direction) momentum distribution for all particles,

$$(1/m_T)dN/dm_T=Cm_T/[\mathrm{exp}(m_T/T)\pm 1]$$
(1)
where $`m_T=\sqrt{p_{T}^{}{}_{}{}^{2}+m_{0}^{}{}_{}{}^{2}}`$ is the transverse mass, $`p_T`$ is the transverse momentum, $`m_0`$ is the particle rest mass, $`C`$ is a normalization constant, and $`T`$ is the initial “temperature” of the system, and a gaussian rapidity distribution for mesons,

$$dN/dy=D\mathrm{exp}[(yy_0)^2/(2\sigma _{y}^{}{}_{}{}^{2})]$$
(2)
where $`y=0.5\mathrm{ln}[(E+p_z)/(Ep_z)]`$ is the rapidity, $`E`$ is the particle energy, $`p_z`$ is the longitudinal (along the beam direction) momentum, $`D`$ is a normalization constant, $`y_0`$ is the central rapidity value (mid-rapidity), and $`\sigma _y`$ is the rapidity width. Two rapidity distributions for baryons have been tried: 1) flat and then falling off near beam rapidity and 2) peaked at central rapidity and falling off until beam rapidity. Both baryon distributions give about the same results. The initial space-time of the hadrons for $`b=0`$ fm (i.e. zero impact parameter or central collisions) is parameterized as having cylindrical symmetry with respect to the beam axis. The transverse particle density dependence is assumed to be that of a projected uniform sphere of radius equal to the projectile radius, $`R`$ ($`R=r_0A^{1/3}`$, where $`r_0=1.12`$ fm and $`A`$ is the atomic mass number of the projectile). For $`b>0`$ (non-central collisions) the transverse particle density is that of overlapping projected spheres whose centers are separated by a distance b. The longitudinal particle hadronization position ($`z_{had}`$) and time ($`t_{had}`$) are determined by the relativistic equations Bjorken:1983a ,

$$z_{had}=\tau _{had}\mathrm{sinh}y;t_{had}=\tau _{had}\mathrm{cosh}y$$
(3)
where $`y`$ is the particle rapidity and $`\tau _{had}`$ is the hadronization proper time. Thus, apart from particle multiplicities, the hadronization model has three free parameters to extract from experiment: $`\sigma _y`$, $`T`$ and $`\tau _{had}`$. The hadrons included in the calculation are pions, kaons, nucleons and lambdas ($`\pi `$, K, N, and $`\mathrm{\Lambda }`$), and the $`\rho `$, $`\omega `$, $`\eta `$, $`\eta ^{}`$, $`\varphi `$, $`\mathrm{\Delta }`$, and $`K^{}`$ resonances. For simplicity, the calculation is isospin averaged (e.g. no distinction is made among a $`\pi ^+`$, $`\pi ^0`$, and $`\pi ^{}`$). Resonances are present at hadronization and also can be produced as a result of rescattering. Initial resonance multiplicity fractions are taken from Herrmann and Bertsch Herrmann:1995a , who extracted results from the HELIOS experiment Goerlach:1992a . The initial resonance fractions used in the present calculations are: $`\eta /\pi =0.05`$, $`\rho /\pi =0.1`$, $`\rho /\omega =3`$, $`\varphi /(\rho +\omega )=0.12`$, $`\eta ^{}/\eta =K^{}/\omega =1`$ and, for simplicity, $`\mathrm{\Delta }/N=0`$.

The second stage in the calculation is rescattering which finishes with the freeze out and decay of all particles. Starting from the initial stage ($`t=0`$ fm/c), the positions of all particles are allowed to evolve in time in small time steps ($`dt=0.1`$ fm/c) according to their initial momenta. At each time step each particle is checked to see a) if it decays, and b) if it is sufficiently close to another particle to scatter with it. Isospin-averaged s-wave and p-wave cross sections for meson scattering are obtained from Prakash et al. Prakash:1993a . The calculation is carried out to 100 fm/c, although most of the rescattering finishes by about 30 fm/c. The rescattering calculation is described in more detail elsewhere Humanic:1998a .

Calculations are carried out assuming initial parameter values and particle multiplicities for each type of particle. In the last stage of the calculation, the freeze-out and decay momenta and space-times are used to produce observables such as pion, kaon, and nucleon multiplicities and transverse momentum and rapidity distributions. The values of the initial parameters of the calculation and multiplicities are constrained to give observables which agree with available measured hadronic observables. As a cross-check on this, the total kinetic energy from the calculation is determined and compared with the RHIC center of mass energy of $`\sqrt{s}=130`$ GeV to see that they are in reasonable agreement. Particle multiplicities were estimated from the charged hadron multiplicity measurements of the RHIC PHOBOS experiment Back:2000a . Calculations were carried out using isospin-summed events containing at freezeout about 5000 pions, 500 kaons, and 650 nucleons ($`\mathrm{\Lambda }`$’s were decayed). The hadronization model parameters used were $`T=300`$ MeV, $`\sigma _y`$=2.4, and $`\tau _{had}`$=1 fm/c. It is interesing to note that the same value of $`\tau _{had}`$ was required in a previous rescattering calculation to successfully describe results from SPS Pb+Pb collisions Humanic:1998a .

Figure 1 shows normalized pseudorapidity distributions summed over pions, kaons, and nucleons from rescattering calculations for $`b=0,5`$, and 8 fm. The widths of the distributions and the flattening near $`\eta =0`$ is similar to data from PHOBOS Back:2001a . Note that if the initial pion rapidity distribution in the calculation was slightly flattened at $`y=0`$ from the simple Gaussian in Equation 2, the small dip seen in the data at $`\eta =0`$ could be reproduced.

Figure 2 shows $`m_T`$ distributions for pions, kaons, and nucleons from the rescattering calculation for $`b=0`$ fm near midrapidity ($`1<y<1`$) fitted to exponentials of the form $`\mathrm{exp}(m_T/B)`$, where $`B`$ is the slope parameter.

The extracted slope parameters shown in Figure 2 are close in value to preliminary measurements from the STAR experiment for the $`\pi ^{}`$, $`K^{}`$, and anti-proton of $`190\pm 10`$, $`300\pm 30`$, and $`565\pm 50`$ MeV, respectively Adler:2002a . Thus, we see that if all hadrons begin at a common temperature-parameter value of 300 MeV, the hadronic rescattering alone is able to generate enough radial flow to account for the differences in slope among the pion, kaon, and nucleon $`m_T`$ distributions.

Figure 3 shows transverse momentum distributions for pions, kaons, and nucleons from a $`b=8`$ fm rescattering calculation which extend to high-$`p_T`$, i.e. 6 GeV/c. As observed in PHENIX data Zajc:2001a , the pion and nucleon distributions merge for $`p_T>2`$ GeV/c and the kaon distribution crosses that for nucleons at around 1 GeV/c.

The elliptic flow and two-pion HBT observables are also calculated from the freeze-out momenta and space-time positions of the particles at the end of the rescattering stage. The elliptic flow variable, $`v_2`$, is defined as Poskanzer:1998a

$$v_2=cos(2\varphi );\varphi =\mathrm{arctan}(p_y/p_x)$$
(4)
where $`p_x`$ and $`p_y`$ are the $`x`$ and $`y`$ components of the particle momentum, and $`x`$ is in the impact parameter direction and $`y`$ is in the “out of plane” direction (i.e. $`xz`$ is the reaction plane and $`z`$ is the beam direction). The HBT pion source parameters are extracted from the rescattering calculation using the same method as was applied for previous SPS-energy rescattering calculations Humanic:1998a . The Pratt-Bertsch “out-side-long” radius parameterization is used Pratt:1990a ; Bertsch:1989a  yielding the four parameters $`R_{Tside}`$, $`R_{Tout}`$, $`R_{Long}`$, and $`\lambda `$, which represent two mutually perpendicular transverse (to the beam direction) radius parameters, a radius parameter along the beam direction, and a parameter related to the “strength” of the two-pion correlations, respectively.

## III Elliptic Flow results

Figure 4 shows the $`p_T`$ dependence of $`v_2`$ for pions and nucleons extracted from the $`b=8`$ fm rescattering calculation compared with the trends of the STAR measurements for $`\pi ^++\pi ^{}`$ and $`p`$ \+ $`pbar`$ at $`1145\%`$ centrality Adler:2001a , which roughly corresponds to this impact parameter. Figure 5 compares the $`p_T`$ dependence of $`v_2`$ for kaons from the $`b=8`$ fm rescattering calculation with the STAR measurements for $`K_{}^{0}{}_{s}{}^{}`$ at $`1145\%`$ centrality Adler:2002b . As seen, the rescattering calculation values are in reasonable agreement with the STAR measurements. The flattening out of the pion and nucleon $`v_2`$ distributions for $`p_T>2`$ GeV/c is consistant with that seen in STAR and PHENIX results for minimum-bias hadrons Snellings:2001a ; Zajc:2001a  (the kaon $`v_2`$ calculation does not extend higher than 2 GeV/c in Figure 5 due to limited statistics). Thus, the same rescattering mechanism that can account for the radial flow seen in Figures 2 and 3 is also seen to account for the magnitude and $`p_T`$ dependence of the elliptic flow for pions, kaons, and nucleons.

## IV HBT results

The pion source parameters extracted from HBT analyses of rescattering calculations for three different impact parameters, $`b=0`$, $`5`$, and $`8`$ fm, are compared with STAR $`\pi ^{}`$ measurements at three centrality bins Adler:2001b  in Figure 6. Note that the PHENIX HBT results Adcox:2002a  are in basic agreement with the STAR results. The STAR centrality bins labeled “3”, “2”, and “1” in the figure correspond to $`12\%`$ of central, the next $`20\%`$, and the next $`40\%`$, respectively. These bins are roughly approximated by the impact parameters used in the rescattering calculations, i.e. the average impact parameters of the STAR centrality bins are estimated to be within $`\pm 2`$ fm of the rescattering calculation impact parameters used to compare with them. In the left panel, the centrality dependence of the HBT parameters is plotted for a $`p_T`$ bin of $`0.1250.225`$ GeV/c. In the right panel, the $`m_T`$ dependence of the HBT parameters is plotted for centrality bin 3, for the STAR measurments, or $`b=0`$ fm, for the rescattering calculations. Although there are differences in some of the details, the trends of the STAR HBT measurements are seen to be described rather well by the rescattering calculation.

## V Discussion

As shown above, the radial and elliptic flow as well as the features of the HBT measurements at RHIC can be adequately described by the rescattering model with the hadronization model parameters given earlier. The results of the calculations are found to be sensitive to the value of $`\tau _{had}`$ used, as was studied in detail for SPS rescattering calculations Humanic:1998a . For calculations with $`\tau _{had}>1`$ fm/c the initial hadron density is smaller, fewer collisions occur, and the rescattering-generated flow is reduced, reducing in magnitude the radial and elliptic flow and most of the HBT observables. Only the HBT parameter $`R_{Long}`$ increases for larger $`\tau _{had}`$ reflecting the increased longitudinal size of the initial hadron source, as seen in Equation 3. One can compensate for this reduced flow in the other observables by introducing an ad hoc initial “flow velocity parameter”, but the increased $`R_{Long}`$ cannot be compensated by this new parameter. In this sense, the initial hadron model used in the present calculations with $`\tau _{had}1`$ fm/c and no initial flow is uniquely determined with the help of $`R_{Long}`$.

At this point, one can consider the physical significance of the present rescattering model in two different ways. The first way is to accept that it is physically valid in the time range where hadronic rescattering should be valid, e.g. for times later than when the particle density reaches about 1 $`fm^3`$, and to take the initial state hadronization model as merely a parameterization useful to fit the data. Considering the calculation this way, one can at least expect to gain an insight into the phase-space configuration of the system relatively early in the collision (in the calculation 1 $`fm^3`$ occurs at a time 4 fm/c after hadronization). The second way to consider the calculation is to see if it is possible to also physically motivate the initial state hadronization model. An attempt to do this is given below.

In order to consider the present initial state model as a physical picture, one must assume: 1) hadronization occurs very rapidly after the nuclei have passed through each other, i.e. $`\tau _{had}=1`$ fm/c, 2) hadrons or at least hadron-like objects can exist in the early stage of the collision where the maximum value of $`\rho `$ approaches 8 GeV/$`fm^3`$, and 3) the initial kinetic energies of hadrons can be large enough to be described by $`T=300`$ MeV in Equation 1.

Addressing assumption 2) first, in the calculation the maximum number density of hadrons at mid-rapidity at $`t=0`$ fm/c is 6.8 $`fm^3`$, rapidly dropping to about 1 $`fm^3`$ at $`t=4`$ fm/c. Since most of these hadrons are pions, it is useful as a comparison to estimate the effective volume of a pion in the context of the $`\pi \pi `$ scattering cross section, which is about 0.8 $`fm^2`$ for s-waves Prakash:1993a . The “radius” of a pion is found to be 0.25 fm and the effective pion volume is 0.065 $`fm^3`$, the reciprocal of which is about 15 $`fm^3`$. From this it is seen that at the maximum hadron number density in the calculation, the particle occupancy of space is estimated to be less than $`50\%`$, falling rapidly with time. One could speculate that this may be enough spacial separation to allow individual hadrons or hadron-like objects to keep their identities and not melt into quark matter, resulting in a “super-heated” semi-classical gas of hadrons at very early times, as assumed in the present calculation.

Since the calculation takes the point of view of being purely hadronic, it is instructive to consider assumptions 1) and 3) in the context of the Hagedorn thermodynamic model of hadronic collisions Hagedorn:1970a . According to Hagedorn, the mass spectrum of hadrons of mass m increases proportional to $`\mathrm{exp}(m/T_0)`$ in hadronic collisions, where $`T_0=160`$ MeV is the limiting temperature of the system. This seems to contradict the value $`T=300`$ MeV needed in the present case in Equation 1 to describe the data. The Hagedorn model assumes that a) the system comes to equilibrium and b) the details of particle production via direct processes and through resonance decay average out. Neither of these assumptions is necessarily guaranteed at very early times in the collision. The use of the thermal functional form, Equation 1, to set up the initial transverse momenta of the hadrons in the present calculations is convenient but not required. For example, the exponential form $`\mathrm{exp}(m_T/T_e)`$ (where $`T_e`$ is a slope parameter) which does not describe thermal equilibrium, could have equally well been used. This exponential form of the transverse mass distribution was successfully used previously in rescattering calculations to describe SPS data Humanic:1998a .

Assumption 1) can also be motivated by the Color Glass Condensate model McLerran:2002a ; Kovner:1995a . In the usual version of this picture, after the collision takes place the Color Glass melts into quarks and gluons in a timescale of about 0.3 fm/c at RHIC energy, and then the matter expands and thermalizes into quark matter by about 1 fm/c. In the context of the present rescattering calculations, it is tempting to modify the collision senario such that instead of the Color Glass melting into quarks and gluons just after the collision, the sudden impact of the collision “shatters” it directly into hadronic fragments on the same timescale as in the parton senario due to the hadronic strong interactions.

## VI Summary

A simple thermal-like initial state model coupled with a hadronic rescattering calculation is able to adequately describe the large elliptic flow and small HBT radii recently measured at RHIC. A feature of this picture is a very early hadronization time of about 1 fm/c after the initial collision of the nuclei.

###### Acknowledgements.

It is a pleasure to acknowledge Ulrich Heinz, Mike Lisa and Rainer Renfordt for their helpful suggestions regarding this work, and Larry McLerran for illuminating discussions on the Color Glass Condensate model. This work was supported by the U.S. National Science Foundation under grant PHY-0099476.