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# Current-induced two-level fluctuations in pseudo spin-valves (Co/Cu/Co) nanostructures

(October 9, 2003)

## Abstract

Two-level fluctuations of the magnetization state of pseudo spin-valve pillars Co(10 nm)/Cu(10 nm)/Co(30 nm) embedded in electrodeposited nanowires ($``$ 40 nm in diameter, 6000 nm in length) are triggered by spin-polarized currents of $`10^7`$ A/cm2 at room temperature. The statistical properties of the residence times in the parallel and antiparallel magnetization states reveal two effects with qualitatively different dependences on current intensity. The current appears to have the effect of a field determined as the bias field required to equalize these times. The bias field changes sign when the current polarity is reversed. At this field, the effect of a current density of 107 A/cm2 is to lower the mean time for switching down to the microsecond range. This effect is independent of the sign of the current and is interpreted in terms of an effective temperature for the magnetization.

preprint: To be published in Physical Review Letters

Current-induced magnetization switching (CIMS) was predicted by Slonczewski Slonczewski (1996) after a first publication by Berger Berger (1996). Observation of this phenomenon in several sample configurations was reported a few years later : homogeneous Ni nanowires Wegrowe et al. (1999), manganite trilayer junctions Sun (1999) and (Co/Cu/Co) sandwich structures Myers et al. (1999); Tsoi et al. (1998); Grollier et al. (2001); Sun et al. (2002). The potential application of the latter structure as a non-volatile magnetic memory motivates the development of detailed models for the theoretical mechanisms underlying CIMS. Most of the present models Waintal et al. (2000); Heide (2001); Wegrowe (2000); Grollier et al. (2002); Zhang et al. (2002) agree on the fact that the Landau-Lifshitz-Gilbert (LLG) equation can be modified by a current-dependent term. This term acts either as a torque, an effective field or leads to spin transfer by a relaxation process. Two experimental approaches are preferred, sweeping the magnetic field $`H`$ or the applied current $`I`$ in order to obtain $`R(I)`$, $`R(H)`$, $`dV/dI(H)`$ or $`dV/dI(I)`$. Alternatively, observations of the relaxation of the magnetization Wegrowe et al. (2002a); Albert et al. (2002); Myers et al. (2002) provide information on the magnetic energy profile.

Recent experimental work showed that it is possible to produce Two Level Fluctuation (TLF) in spin-valve nanostructures with the injection of a spin-polarized current Myers et al. (2002); Urazhdin et al. (2003). In this paper, the TLF produced by the current are studied in pseudo spin-valves and analyzed in terms of a potential profile composed of two wells separated by a barrier. The applied field can be adjusted so that the potential well is symmetrical. At this field it becomes especially clear that the current enhances the jump rate irrespective of the current sense.

This study focuses on the irreversible part of the hysteresis in a (Co/Cu/Co) pseudo spin-valve burried in the middle of a long Cu nanowire. A uniaxial magnetocrystalline anisotropy can be obtained Wegrowe et al. (2002b). Thus, the spin-valve behaves as a two-state system defined by the two relative orientations of the magnetic layers. The samples were produced by the method of electrodeposition in track-etched membrane templates Fert and Piraux (1999). Gold layers were sputtered on both sides of a porous polycarbonate membrane, the pores left open were filled electrochemically with Co and Cu. Wires of Cu(1000)/\[Co(10)/Cu(10)/Co(30)\]/Cu(4950), about 40 nm in diameter and 6000 nm in length, were obtained. A contact to a single nanowire was established by monitoring the potential between both sides of the membrane during the electrodeposition Wegrowe et al. (1998).

Experiments were performed at room temperature. For characterization purposes, giant magnetoresistance (GMR) of the spin-valve system was measured at low current ($`10^4`$A/cm2). The sample shape insured current-perpendicular-to-the-plane (CPP) geometry. The magnetic field was applied in the direction parallel to the plane of the Co layers. The GMR results showed a hysteretic behaviour with abrupt steps between two resistance values $`R^p`$ and $`R^{ap}`$ ($`\mathrm{\Delta }R=R^{ap}R^p`$ is typically 1 $`\mathrm{\Omega }`$ or $`\mathrm{\Delta }R/R_{wire}=`$ 0.18%) corresponding to the switching of the relative magnetization orientation of the ferromagnetic layers (dashed lines in Fig. 1). The abrupt single transitions between these two orientations suggest single domain structures.

Hysteresis measurements were also performed under large DC currents ($`10^7`$ A/cm2). Large currents affect the field range over which the spin valve is in the antiparallel state. This range increases with increasing positive currents $`I^+`$ (full line in Fig. 1(a)) and decreases with negative currents $`I^{}`$ (full line in Fig. 1(b)). The positive current is defined as the one for which electrons flow from the thin to the thick magnetic layer (in contrast to the definition of Ref. Grollier et al. (2001)). For each current $`I^+`$ or $`I^{}`$, we determined the magnetic field $`H_{sw}^{pap}`$ at which a parallel to antiparallel transition occurred. The time-domain measurements were carried out as follows. A saturation field of 1 T was established and swept down with a rate of 0.05 T/s to the measurement field $`H`$ in the vicinity of $`H_{sw}^{pap}`$. At this field value $`H`$, a current pulse was applied, of amplitude $`I`$ and of 8 $`\mu `$s duration. The resistance was recorded as a function of time. For a broad range of applied fields, the spin valve system presented TLF between $`R^p`$ and $`R^{ap}`$ (Fig. 2). The apparent intermediate steps in Fig. 1 as well as the fluctuations that appears in Fig. 2 are nothing but noise. The stochastic nature of this process was assessed by determining the histograms of the residence times $`\tau _{ap}`$ or $`\tau _p`$ before each transition. They presented an exponential distribution (inset of Fig. 2) from which the characteristic times $`\tau _{ap}`$ and $`\tau _p`$ could be extracted.

For each current value, the protocol was repeated for several values of $`H`$ until $`H`$ was so far from $`H_{sw}^{pap}`$, that the fluctuations were too scarce. This measurement process was repeated for several current values (either positive or negative). This protocol and the measurement setup implies two limiting currents: the lowest current is the one that allows the observation of at least one magnetization switching (p $``$ ap $``$ p) in the interval time of 8 $`\mu `$s, and the highest current is the one for which the switching rate is below the bandwidth of the measurement setup, 25 MHz. We collected data of average times versus field and current $`\tau _p/\tau _{ap}`$ (Fig. 3) at fields around the p $``$ ap transition seen in the high current GMR curves (Fig. 1). We have carried out a detailed study of the TLF around the transition $`H_{sw}^{pap}`$.

We can assume that the thick Co layer remains fixed because we restricted the magnetic field values to a small enough range. The metastable characteristics of the magnetization of the thin Co layer can be described by the Néel-Brown activation process Coffey et al. (1998a). The energy barrier depends on the shape and magnetocrystalline anisotropy, on the external field and on the dipole field due to the pinned layer Wegrowe et al. (2002b). At low current, the spin-valve is stable and does not show TLF. The effective barrier when the double well is symmetric can be estimated to be of the order of several thousands Kelvin Wernsdorfer et al. (1995). Therefore the TLF at large current cannot be ascribed to Joule heating and must arise from spin polarization of the current.

The mean time to escape from a local energy minimum $`i`$ over an effective barrier into another local minimum $`j`$, where $`\{i,j\}=\{p,ap\}`$ or $`\{ap,p\}`$ (inset in Fig. 4), can be written in the form of an Néel-Brown law Coffey et al. (1998b)

$$\tau _i=\tau _0\mathrm{exp}\left(\frac{E^{ij}(H)}{k_BT}\right)$$
(1)
where $`E^{ij}`$ is the energy maximum of the barrier measured from the local minimum $`i`$ and $`\tau _0`$ the waiting time at zero energy barrier. The value of $`\tau _0`$ we choose is not critical for the outcome of our analysis. We set it at $`\tau _0`$ 0.1 ns as a reasonable order of magnitude.

We report in Fig. 4 the value of the magnetic field $`H_{sym}(I)`$ applied at each current $`I`$ in order to obtain a symmetric profile, that is, when $`\tau _{ap}/\tau _p=1`$. The bias field necessary to make the magnetic potential well symmetric is a monotonic, almost linear function of the current. Here, the effect of a positive current appears as a positive bias field, since a negative field must be applied to compensate for it so as to keep the well symmetric. A positive bias field corresponds to a tendency to remain in the antiparallel state. This is equivalent to the hysteresis widening of Fig. 1.

Our data show that the effect of the current is not simply a biasing of the potential profile. We find that, at the field $`H_{sym}(I)`$, the mean time $`\tau _{ap}=\tau _p`$ decreases with the absolute value of the current as shown in Fig. 5. Hence, this effect is qualitatively different than the dependence $`H_{sym}(I)`$.

We discuss now the possible interpretations that may account for our observations of $`H_{sym}(I)`$ and $`\tau _{ap}(I)`$ when $`\tau _{ap}=\tau _p`$. Assuming the injection of spin-polarized current Slonczewski (1996), the LLG equation can be written as Li and Zhang (2003)

$`{\displaystyle \frac{d𝑴}{dt}}=`$ $`\gamma 𝑴\times 𝑯_{eff}+{\displaystyle \frac{\alpha }{M_s}}𝑴\times {\displaystyle \frac{d𝑴}{dt}}`$ (2)
$`+{\displaystyle \frac{\gamma a_J}{M_s}}𝑴\times \left(𝑴\times \widehat{𝑴}_p\right),`$
where $`𝑴`$ is the magnetization of the free layer, $`\gamma `$ is the gyromagnetic factor, $`𝑯_{eff}`$ the effective field, including the applied field, anisotropy field, demagnetizing field and random fields (caused by thermal fluctuations), $`\alpha `$ the Gilbert damping factor, $`M_s`$ the magnetization value at saturation, $`a_J`$ the dependence of the current-driven torque on the applied current, and $`\widehat{𝑴}_p`$ a unit vector representing the magnetization orientation of the pinned layer. It has been shown that the Néel-Brown’s relaxation formula can be applied by introducing an activation energy defined as the difference between the true energy barrier and the work done by the current-driven torque Li and Zhang (2003). Depending on the current, this work can be either positive or negative. This point of view fits with our observation of $`H_{sym}(I)`$ which is positive or negative depending on the polarity. However this model cannot account for the positive slope at negative current (Fig. 5). Therefore we need to turn to another mechanism to explain $`\tau _{ap}(I)`$ when $`\tau _{ap}=\tau _p`$.

Several authors have considered the excitation of spin waves by current Tsoi et al. (2002); Rezende et al. (2000). Here, we estimate the effect of the excitation of spin waves caused by the injection of spin polarized currents in terms of an effective magnetization temperature, an idea simultaneously raised by Urazhdin et al. Urazhdin et al. (2003). Electrons are injected in the thin layer with a polarization $`\beta `$. Spins of electrons with $`s`$ character are rapidly relaxed via spin-orbit scattering, while spins of $`d`$ electrons relax as the magnetization. Each $`d`$ electron carries one Bohr magneton whose relaxation produces, on average, the equivalent of one magnon. Hence the time rate of generation of magnons by a current $`I`$ is counted to be $`\alpha _d\beta (I/e)`$, where $`\alpha _d`$ is thought of as a coefficient between 0 and 1 that represents the proportion of $`d`$-type conduction electrons. In the order of magnitude estimate below, we take $`\alpha _d=4`$%, $`\beta (I>0)`$ = 40% and $`\beta (I<0)`$ = 27%. The dependence of $`\beta `$ on the sense of the current can be expected since the spin-valve is asymmetric Zhang et al. (2002).

Magnetic resonance studies of the bottleneck effect Bloembergen (1950); Kittel and Mitchell (1956) tell us that $`d`$ electrons relax on a time scale $`\tau _d`$ of the order of 1 ns. So the average number of magnons follows a rate equation

$$\frac{dn}{dt}=\frac{n}{\tau _d}.$$
(3)
The current pulse is very long compared to magnetization dynamics. Since we detect TLF over a time scale of microseconds, the magnetic excitations have reached a stationary state out of equilibrium. The average number of magnons is the one that balances the generation of magnons by the current and their relaxation to the lattice

$$\frac{n}{\tau _d}=\alpha _d\beta \frac{I}{e}.$$
(4)
The average number of spin-waves at a temperature $`T_m`$ follows a Bose-Einstein distribution $`\left[\mathrm{exp}(\mathrm{}\omega /k_BT_m)1\right]^1`$. Taking the spin wave dispersion relation $`\mathrm{}\omega (k)2JSa^2k^2`$, where $`𝒌`$ is the wave vector and $`a`$ the lattice constant, the density of magnons at this temperature can be estimated from Aharoni (2000)

$$\frac{1}{V}\underset{k}{}n_k=\frac{1}{(2\pi )^2}\left(\frac{k_BT_m}{2JSa^2}\right)^{3/2}\frac{1}{2}\sqrt{\pi }\zeta \left(3/2\right),$$
(5)
where the stiffness constant $`2JSa^2`$ is of the order of 5 meV$``$nm2 for Co, and the Zeta function $`\zeta \left(3/2\right)=2.61`$. We can account for the data of Fig. 5 by assuming that this random, incoherent generation of magnons gives rise to a magnetic state of excitation characterized by a temperature $`T_m`$ calculated with Eq. 4 and 5. The mean times are assumed to follow

$$\tau _{ap}(I)=\tau _p(I)=\tau _0\mathrm{exp}\left(\frac{E_0}{k_BT_m(I)}\right),$$
(6)
with $`E_0=6^{}300`$ K, a reasonable value for a Co layer of this size Wernsdorfer et al. (1995). Thus we can account for our data (Fig. 5) with a variation of the effective temperature $`T_m(I)`$ from about 500 K to 1100 K.

In conclusion, we have measured the current dependence of the magnetic energy profile of a (Co/Cu/Co) nanopillar. Positive current shifts the field range over which the TLF zone is seen to more positive magnetic fields, while negative current shift it to more negative fields. However, both current directions decrease the jump rate. Consequently, these two qualitatively different features cannot be accounted for with a current dependent effective torque only. Instead, it appears that an irreversible transfer of magnetic momentum occurs, leading to spin-wave excitations.

We acknowledge support from the Swiss NSF through grant 200020-100271, from EC grant EuNITT PPRN-CT-2000-00047 through OFES 99.0141 and EC grant NEXT IST-2001-37334 through OFES 02.0265.


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# Do Ordinary Nuclei Contain Exotic States of Matter?

## 1 Inclusive Scattering from Nuclei at $`x>1`$

Inclusive scattering from nuclei at $`x>1`$ has provided a great deal of information about the high momentum components of the nuclear wave function. Measurements at large momentum transfer, $`q`$, and small energy transfer, $`\nu `$, are dominated by quasielastic scattering from single nucleons. This process is sensitive to the elastic electron-nucleon cross section and the distribution of nucleons within the nucleus. For a stationary nucleon, elastic scattering corresponds to $`x_{Bjorken}=Q^2/2m_N\nu =1`$, where $`m_N`$ is the mass of the nucleon and $`Q^2=q^2\nu ^2`$. Nucleons with a large initial momentum parallel (anti-parallel) to the exchange photon occur at $`x>1`$ ($`x<1`$). By selecting low energy transfers, corresponding to $`x>1`$, there is little background from inelastic processes, and the measurements are sensitive to the distribution of nucleons with large momenta.

These high momentum components come from short-range correlations (SRCs) in the nucleus. These correlations are an important part of nuclear structure and are related to the short-range, strongly repulsive core of the N-N interaction. Comparisons of inclusive scattering from heavy nuclei and deuterium provided one of the first experimental signatures of short-range range correlations in nuclei . Above $`x1.5`$, the cross section behavior was identical for all nuclei measured, yielding a plateau in the $`A/D`$ ratio and indicating that the same two-nucleon correlations that generate the high-momentum nucleons in the deuteron are also the dominant source of high-momentum nucleons in heavy nuclei. Subsequently, short-range correlations in nuclei have been probed in a variety of reactions including A(p,2p), A(e,e’p), A(e,e’NN).

Completed and planned measurements  at Jefferson Lab up to 6 GeV will map out the strength of two-nucleon short-range correlations in nuclei. These measurements will also provide a first look at high-$`Q^2`$ cross sections for $`2.5x<3`$, where the cross section is most sensitive to the presence of multi-nucleon correlations. Figure 1 shows the structure function per nucleon for iron compared to a mean-field calculation, a calculation including two-nucleon SRCs , and one including multi-nucleon SRCs . The 4 GeV data are consistent with two-nucleon SRCs, while future measurements at 6 GeV  will significantly increase the sensitivity to multi-nucleon correlations, extending the $`Q^2`$ range at $`x=1.5`$ to more than 10 GeV2. Even higher beam energies will dramatically increase both the $`x`$ and $`Q^2`$ range of the data. With the increased $`x`$ coverage possible with an 11 GeV beam at Jefferson Lab, these studies can be extended to isolate and map out the strength of multi-nucleon correlations.

In addition to improving the sensitivity to multi-nucleon correlations, higher energies will also provide a new way to study two-nucleon correlations by allowing us to probe the quark structure of two-nucleon correlations. A measurement in the deep inelastic scattering regime at $`x>1`$ would allow us to measure for the first time the distributions of superfast quarks in nuclei, where the struck quark carries more momentum than an entire nucleon.

There is little data available for structure functions of nuclei at $`x>1`$. Measurements of muon scattering from iron  have only upper limits above $`x=1.1`$, and show a rapid falloff in the structure function near $`x=1`$ ($`F_2e^{16.5x}`$). Measurements of neutrino scattering from carbon  also have a limited $`x`$ range ($`x<1.2`$), but indicate significantly more strength at large $`x`$ ($`F_2e^{8.3x}`$). With the increase in $`Q^2`$ possible with the JLab energy upgrade, high precision measurements of the structure function over a wide range in $`x`$, allowing us to cleanly map out the distribution of superfast quarks. At the $`Q^2`$ values achievable with the JLab upgrade, the inelastic cross section dominates even for $`x>1`$, and we should be able to extract the structure function in the scaling regime up to $`x1.4`$.

## 2 High-density Configurations

These high-$`x`$ quark distributions are intrinsically related to the quark structure of the two-nucleon correlations. Fig. 1 demonstrates that for large $`x`$ and $`Q^2`$, the scattering is dominated by scattering from these short-range configurations. These quark distributions probe the internal structure of high-density configurations, where nucleons have significant overlap. The EMC effect demonstrates that the quark structure of a nucleus is more than just a convolution of the quark structure of its nucleons. If this comes from density-dependent modifications to nucleon structure, then a similar but much larger effect should be seen when one examines the quark distributions at large $`x`$, where the strength comes almost entirely from nucleon pairs that are nearly overlapping .

Such a modification of hadron structure is expected at high densities. Figure 2 shows the phase diagram for nuclear matter. At high densities, just as at high temperature, there is a phase transition from hadronic matter to quark matter. While ordinary nuclear densities are well below this transition, the densities achieved in overlapping nucleons may be high enough to see the effect of this phase transition. Thus, the EMC effect may not arise from the increase in average nuclear density but instead a be result of large changes in the structure of the high-density components arising from short-range correlations.

Figure 3 illustrates the overlap of nucleons separated by 1.7 fm, the average separation in nuclear matter, and 0.6 fm. The short-range repulsive core of the N-N interaction becomes very large below $``$0.4 fm, so the separation of the nucleons in the correlated pair should be larger than this distance. At 0.6 fm, the peak densities are several times normal nuclear matter densities.

At these densities, there may be a significant change in the structure of the nucleon, which will manifest itself in a modified quark distributions. Figure 4 shows the quark distribution for a deuteron made of just two nucleons (dashed line), and with a 5% contribution from a 6-quark bag (solid line). For $`x<1`$, there is almost no difference in the quark distributions, but for $`x>1`$ the small 6-quark component dominates the quark distribution. While this is just one model for nuclear effects at high density, a significant increase in the distribution of superfast quarks is a fairly general signature of such modifications. In a nucleon at rest the quarks share its momentum, and thus cannot have a momentum fraction, $`x`$, larger than one. In nuclei, quarks can gain additional momentum from the interaction of the nucleons. Even taking into account the high-momentum tails of the nucleon distributions coming from SRCs, the quark distribution falls off extremely rapidly for $`x>1`$. However, if the nucleons in the SRCs have significant overlap, the quarks can directly share their momentum, allowing for a much greater probability of finding a single quark with a very large momentum fraction. Such an observation would be a clear signature of deviations from the purely hadronic picture of nuclei.

## 3 Conclusions

Measurements of inclusive scattering from nuclei at $`x>1`$ probe the high-momentum components of the nuclear wavefunction. These high momentum nucleons arise from the short-range interaction of nucleon pairs. At moderate energy scales, where the scattering is dominated by quasielastic scattering from individual nucleons, these nucleon pairs can be kinematically isolated in inclusive reactions. High energy measurements will allow us to probe the quark structure of these short-range correlations, and look for modification to the underlying quark structure of hadrons in regions where the instantaneous densities are several times the density of normal nuclear matter. The structure of nucleons and the distribution of high-momentum quarks may be substantially altered in this region, where significant overlap of nucleons should allow direct interaction between quarks in different nucleons. Studies of these high-density configurations will allow us to determine if such modifications of nucleon structure are responsible for the EMC effect, and will help us understand the quark-gluon phase transition at high density. This complements RHIC studies of this same transition at high temperature, while at the same time providing us information on the structure of matter at extremely high densities. Probing these high density components in nuclei is the only way to directly study high density nuclear matter, and what we learn here will be important in understanding neutron stars and other compact astronomical objects.

## Acknowledgments

This work is supported by the U.S. Department of Energy, Nuclear Physics Division, under contract W-31-109-ENG-38.


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# Exact Born Approximation for the Spin-Boson Model

## Appendix A Scaling form for branch cut integrals

By numerical study we find that the branch cut integrals conform to some simple scaling laws for small $`\alpha `$. If we write the bc1 and bc2 integrals as $`z_{bc1}(t)=_0^{\mathrm{}}𝑑xe^{q_1xt}z_{bc1}(s=q_1x)`$ and $`z_{bc2}(t)=\mathrm{Re}_E^{\mathrm{}}𝑑xe^{ixt}z_{bc2}(s=ix)`$, then we find that for small $`\alpha `$ and for $`s<<\omega _c`$, $`z_{bc1}(s)`$ can be written in a scaling form

$$z_{bc1}(x)=(\alpha /E)f_1(ϵ/\mathrm{\Delta },x/E).$$
(25)
But for bc2 a very different scaling law applies:

$$z_{bc2}(x)=(1/E)f_2(ϵ/\mathrm{\Delta },(xE)/\alpha E).$$
(26)
Here $`f_{1,2}`$ are dimensionless, “universal” functions that govern the behavior of the branch cut contributions for small $`\alpha `$. For bc1, the behavior that the scaling law gives is very simple: Eq. (25) implies that $`z_{bc1}(t)=\alpha \overline{f}_1(ϵ/\mathrm{\Delta },Et)`$, where $`\overline{f}_1`$ is the Laplace transform of the scaling function $`f_1`$. We might have expected this behavior from Eq. (20), from which we can read off the scaling function for $`ϵ=0`$. In fact it appears from numerical studies that $`f_1`$ hardly changes as $`ϵ`$ is varied, except for an overall scale factor; that is, $`\overline{f}_1(ϵ/\mathrm{\Delta },Et)a(ϵ/\mathrm{\Delta })b(Et)`$. We find that the scaling function $`a(\tau )>0`$ is peaked at $`\tau =0`$. So, the memory effect described above for $`ϵ=0`$ persists for finite $`ϵ`$, but becomes smaller. For $`|ϵ|\mathrm{\Delta }`$ the bc2 contribution, which we will describe now, becomes dominant over the bc1 one.

Returning to Eq. (26), if we write the Fourier transform of the scaling function as $`\overline{f}_2(\tau )=_0^{\mathrm{}}e^{ix\tau }f_2(x)𝑑x`$ and consider its polar form $`\overline{f}_2(\tau )=r_2(\tau )e^{i\varphi _2(\tau )}`$, then we obtain

$$z_{bc2}(t)=\alpha r_2(\alpha Et)\mathrm{cos}(Et+\varphi _2(\alpha Et)).$$
(27)
This shows that bc2 contributes an oscillatory part to the solution, whose “$`T_2`$” decay is determined by the features of the scaling function $`r_2`$. A few more observations about $`f_2`$ (obtained initially from numerical study) reveal some crucial properties of the $`r_2`$ function: 1) $`f_2(0)=0`$; 2) $`|f_2(x)|`$ has a single maximum at $`x=x_0`$, where $`x_0`$ is some constant of order unity; 3) Most important for the present discussion, for $`x>x_0`$ $`f_2(x)`$ approaches $`1/x`$, that is, $`f_2(x)x_1/x`$, where $`x_1`$ is another real constant of order unity. Fact 3) implies that, for $`\tau 0`$, $`r_2(\tau )x_1\mathrm{log}(x_0\tau )`$. That is, we conclude that at sufficiently short time (actually for $`t1/(\alpha Ex_0)`$, so a relatively long time),

$$z_{bc2}(t)=\alpha x_1\mathrm{log}(x_0\alpha Et)\mathrm{cos}(Et+\varphi ),$$
(28)
as stated in the text.


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# Separation Between Antiferromagnetic and Ferromagnetic Transitions in Ru1-xCuxSr2EuCu2O8+δ

## Abstract

The macroscopic magnetizations of Ru1-xCuxSr2EuCu2O8+δ with $`x`$ between 0 and 0.15 were investigated. A ferromagnet-like transition as well as an antiferromagnet-like transition appear around $`T_M`$ in the low-field magnetization and around $`T_{AM}`$ in the high-field differential susceptibility, respectively. The separation between them, which is accompanied by a flat plateau in the magnetic $`C_p`$, increases with $`x`$. Superparamagnetic $`M(H)`$ and slow spin dynamics, i.e. characteristics of nanomagnetic clusters, were observed far above $`T_M`$. A comparison with RuSr2(Eu1-yCey)Cu2O10+δ and some manganites further suggests that a phase separation occurs, which can describe well the conflicting magnetic-superconductivity data previously reported.

The puzzling bulk, yet granular, superconductivity (SC) in rutheno-cuprates RuSr2RCu2O8+δ (Ru1212R) and RuSr2(R,Ce)2Cu2O10+δ (Ru1222R) with R = Gd, Eu, or Y,fel ; ber ; tal ; xue  which coexists with a weak ferromagnetism (FM), is closely related to their magnetic structure. While a homogeneous canted antiferromagnetic (CAFM) spin-order may coexist with more-or-less ordinary superconductivity, such as the proposed Meissner state or the $`\pi `$-phase SC,ber ; pic  magnetic inhomogeneity at length scales $`\xi `$ will unavoidably lead to a Josephson-junction-array-like superconductivity,xue  where $`\xi `$ is the coherence length. In the case of Ru1222R, the reported data seem to indicate a rather complicated magnetic structure. Both the AFM-like differential-susceptibility maximum of the Ru ($`\chi _{Ruonly}`$) and the hyperfine splitting of the Mössbauer spectra, for example, occur at temperatures almost two times higher than the $`T_M`$, where an FM-like transition occurs in the low-field field-cooled magnetization ($`M_{FC}`$).fel ; xue2  Either a phase separation or a multistage transition, therefore, should occur.fel ; xue2  On the other hand, the situation of Ru1212R has been suggested to be different. The inflection point $`T_{AM}`$ at $`^2(T\chi _{Ruonly})/T^2=0`$, which should be the Néel temperature in simple antiferromagnets,fis  and the $`T_M`$ are in rough agreement for a Ru1212Eu sample.but  Mean-field-like scaling has also been observed below $`T_M`$ by both neutron powder diffraction (NPD) and zero-field nuclear magnetic resonance (ZFNMR).lyn ; tok  It is therefore natural that a simple CAFM was assumed in many previous investigations. This model, however, faces a dilemma in accommodating the magnetizations and the ZFNMR and NPD data. The NPD, for example, indicated that the Ru spins are AFM-aligned (G-type) along the $`c`$ axis with a very tight upper limit of the FM components, i.e. $`<0.1`$ and $`0.2`$ $`\mu _B`$/Ru at $`H=0`$ and 0.4 T $`H`$ 7 T, respectively.lyn  The spontaneous magnetization of the sample, however, reaches $`M_r800`$ emu/mole, i.e. an FM component 0.28 $`\mu _B`$/Ru at $`H=0`$. The extrapolated zero-field magnetization of 0.6 $`\mu _B`$/Ru at 50 K,but  which may serve as a lower limit for the FM component at 5 T, is again three times larger. The ZFNMR data, in addition, demonstrate that the Ru-spins should be aligned perpendicular to the $`c`$ with a major (or dominant) FM component.tok  This unusual magnetic structure, which appears as G-type AFM along $`c`$ in NPD but ordered along $`a,b`$ with a large FM component in both magnetization and NMR, suggested that the magnetic structure of Ru1212R deserved a reexamination. It should be pointed out that both the extremely broad $`C_p`$ peak and the superparamagnet-like $`M(H)`$ up to 2 $`T_M`$ in Ru1212Gd already suggest that its magnetic transition is far from simple:tal ; but  the spin correlations may exist up to 2 $`T_M`$ with a significant entropy and a correlation size as large as $`10^2`$$`10^3`$ $`\mu _B`$,xue2  both being characteristic of phase separation. It is interesting to note that both $`T_M`$ and $`T_{AM}`$ of Ru1212R can be tuned by Cu-doping.kla  The evolutions of $`M`$, $`\chi _{Ruonly}`$, and $`C_p`$ of Ru1-xCuxSr2EuCu2O8+δ with $`0x0.15`$, therefore, were measured. The $`T_M`$ drops more than 25 K with $`x`$ while the variation in $`T_{AM}`$ is negligibly small. A separation between $`T_M`$ and $`T_{AM}`$ is developed with $`x`$. This separation is further accompanied by a magnetic $`C_p/T`$ with a flat plateau between $`T_M`$ and $`T_{AM}`$. Hence, a mesoscopic phase-separation is suggested.

Ceramic Ru1-xCuxSr2EuCu2O8+δ samples with $`x`$ between 0 and 0.15 were synthesized following the standard solid-state-reaction procedure. Precursors were first prepared by calcinating commercial oxides at 600–900 C under flowing O2 at 1 atm. Mixed powder with a proper cation-ratio was then pressed into pellets and sintered at 960 C. The final heat treatment was done at 1065–1070 C for 7 d in oxygen after repeatedly sintering and regrinding.xue  The structure of the samples was determined by powder X-ray diffraction (XRD) using a Rigaku DMAX-IIIB diffractometer. The $`x`$ dependence of the lattice parameters, i.e. the $`c11.553(2)`$ to 11.550(2) Å for $`x=0`$ and 0.15, respectively, is slightly weaker than that reported for Ru1-xCuxSr2GdCu2O8+δ.kla  Minor impurity phases, likely SrRuO3 or oxides of (Sr,Cu), are below 5% at $`x0.15`$ (Fig. 1). The composition was measured by a JEOL JXA 8600 electron microprobe with attached wavelength dispersive spectrometers (WDS). The local inhomogeneity of $`1x`$ is within the experimental resolution of $`\pm 0.05`$.lor  The magnetizations were measured using a Quantum Design SQUID magnetometer with an $`ac`$ attachment and the specific heat was measured in a Quantum Design PPMS with a specific-heat attachment.

Superconductivity appears in all the samples below a critical temperature $`T_c`$ 20–30 K. A single-step jump of $`M_{FC}`$ also appears with cooling at a higher temperature (Fig. 2a). According to the scaling correlation $`(HM_0/MH_0)^{1/\gamma }=t+(M/M_0)^{1/\beta }`$, the $`M/T`$ of an ideal ferromagnet should decrease with $`t=(TT_M)/T_M`$ as $`1/t^{\gamma +1}`$ above $`T_M`$, but increase as $`(t)^{1\beta }`$ below, where $`0<\beta <1`$, $`\gamma >0`$, $`H_0`$, and $`M_0`$ are two critical exponents and two critical amplitudes, respectively. The situation for a CAFM magnet should be similar. Therefore, the inflection point of $`M_{FC}(T)`$ at 5 Oe, i.e. the temperature at which $`M_{FC}/T`$ peaks, is used as the $`T_M`$ (Fig. 2a). The well defined $`T_M`$ and the large FM component below $`T_M`$ are in rough agreement with those reported for Ru1212Eu,but  but rather different from those of Ru1-xCuxSr2GdCu2O8+δ,kla  where no clear FM transition can be identified with $`x0.1`$. Differences in both the rare-earth elements and the synthesis procedures may contribute to the variation. It should be pointed out that the well defined $`T_M`$ and the large $`M_{FC}`$ of our samples make the analysis of $`M_{FC}`$ and $`C_p`$ easier and without significant interference from the minor impurities. A systematic decrease of $`T_M`$ with $`x`$ is observed, e.g. $`T_M134`$ K and 117 K at $`x=0`$ and 0.1, respectively (Fig. 2a). It is also interesting to note that the reported bifurcation point between $`M_{ZFC}`$ and $`M_{FC}`$, which should be very close to $`T_M`$ if the domain pinning is strong, in Ru1-xCuxSr2GdCu2O8+δ shows almost the same $`x`$ dependence, i.e. down to $`115`$ K and 100 K with $`x=0.1`$ and 0.2, respectively.kla

The $`\chi =M/H`$ of a simple AFM magnet, which will be $`H`$-independent far above its AFM transition, should have a maximum slightly above the Néel temperature, $`T_{AM}`$. It has been suggested, in fact, that the magnetic energy, $`E_m`$, and $`\chi `$ should both depend on the pair correlation functions $`\mathrm{\Gamma }(r)=3[S^z(0)S^z(r)]/S(S+1)`$ as $`E_m\mathrm{\Gamma }_1`$ and $`\chi [1+\mathrm{\Sigma }_r\mathrm{\Gamma }(r)]/T[1+f(T)\mathrm{\Gamma }_1]/T`$, where $`\mathrm{\Gamma }(r)`$, $`\mathrm{\Gamma }_1`$, and $`f(T)`$ are the pair-correlation with the pair distance $`=r`$, the correlation with the nearest-neighbor, and a slowly varying function of $`T`$, respectively.fis  This leads to an approximation of $`C_p(T\chi )/T`$ if the short-range correlation $`\mathrm{\Gamma }_1`$ is dominant. $`T_{AM}`$, therefore, can be defined as the temperature of the $`(T\chi )/T`$ peak,fis  which is observed close to the $`\chi `$-maximum temperature in 3D but much lower in 2D.jon  For CAFM magnets, an FM-like $`M_{FC}`$ step may coexist with a $`(T\chi )/T`$ peak. However, $`T_{AM}T_M`$ is expected, except for the possible $`H`$-induced transition shifts.note

To analyze the magnetization of Ru1-xCuxSr2EuCu2O8+δ, the Eu/CuO2 contributions were first eliminated using the procedure previously proposed,but  i.e. with a Van Vleck susceptibility of free Eu3+ and a $`T`$-independent $`\chi _0`$ of $`8.7\times 10^4`$ emu/mole for CuO2. For the undoped sample with $`x=0`$, the Ru contribution is $`H`$-independent and follows a Curie-Weiss (C-W) fit only above 250 K with a C-W constant $`2.6`$ $`\mu _B`$/Ru and a Curie temperature of 127 K. Deviation from the C-W fit and large superparamagnetic $`M(H)`$, however, develop at lower temperatures (Fig. 2a). The Ru contribution to $`\chi `$ at 1 T, for example, is more than 10% higher than that expected between 180 K and $`T_{AM}`$ (Fig. 2a), indicating a dominant FM interaction. The 5 T differential Ru-susceptibility after subtracting the Eu/CuO2 contributions ($`\chi _{Ruonly}`$), however, shows an opposite downturn, suggesting significant AFM interactions (Fig. 2a). In particular, a minimum of $`1/\chi _{Ruonly}`$ and a $`(T\chi )/T`$ peak appear around 157 K (Fig. 2a) and $`T_{AM}138`$ K (Fig. 2b), respectively, for the $`x=0`$ sample. Undoped Ru1212Eu, therefore, might be interpreted as a simple CAFM by either ignoring the 4 K difference between $`T_M`$ and $`T_{AM}`$,but  or by regarding it as a small $`H`$-induced transition shift.

To further confirm the presumed $`T_{AM}`$, the magnetic specific heat was measured at a zero field using a nonsuperconducting YBa2(Cu2.73Zn0.27)O7 (YBCO) ceramic as the reference (Fig. 2b). The raw specific heat of Ru1212 is well above that of YBCO between 80 and 180 K, but the two merge outside this region, a situation similar to the data of Ru1212Gd.tal  The magnetic $`C_p/T`$, i.e. the difference between Ru1212R and YBCO, shows a well defined peak at 133 K, which is only slightly lower than the 138 K $`(T\chi )/T`$ peak observed. This agreement between the $`C_p/T`$ peak at zero field and the $`(T\chi )/T`$ peak at 5 T again demonstrates that the procedure of Fisherfis  works reasonably well and that the $`H`$-induced transition shift is small in our case. It is also interesting to note the high-$`T`$ tail of $`C_p/T`$ and the non-C-W magnetization up to 180 K or higher (Figs. 2a,b). Significant short-range spin orders, therefore, should occur far above $`T_M`$ and $`T_{AM}`$.

With the Cu doping, however, the $`T_M`$ and the $`T_{AM}`$ evolve in different ways and the separation between them broadens. At $`x=0.1`$, for example, the $`T_M`$ is quickly suppressed to 117 K but the $`(T\chi )/T`$ peak remains at 138 K (Figs. 2a,b). The accompanying $`C_p/T`$ appears to broaden with $`x`$ as well (Fig. 2b). In particular, the well defined peak evolves into a flat plateau between $`T_M`$ and $`T_{AM}`$ (Fig. 2b). It should also be pointed out that the separation at $`x=0.1`$ is larger than the transition width in $`M_{FC}`$. Neither the sample inhomogeneity nor the experimental resolution, therefore, can account for the separation (Figs. 2a,b). The AFM-like $`(T\chi )/T`$ peak and the FM-like $`M_{FC}`$ jump seem to carry distinct spin entropies of comparable strength.

It is therefore interesting to compare the data with that of Ru1222R, where two separate transitions have been observed in both magnetizations and Mössbauer spectra.fel ; xue2  The $`T_M`$ and $`T_{AM}`$ of Ru1-xCuxSr2EuCu2O8+δ samples with $`0x0.15`$, the O2/Ar-annealed RuSr2(Gd1.4Ce0.6)Cu2O10+δ, and two as-synthesized Ru1222Eu samples are shown in Fig. 2c.xue2  The separation $`T_{AM}T_M`$ increases systematically with decreasing $`T_M`$ in the Cu-doped Ru1212Eu: from an extrapolated zero-separation at $`T_M140`$ K to 25 K at $`T_M110`$ K, where the data smoothly evolve into that of Ru1222R (Fig. 2c). The observation of $`T_{AM}=T_M`$ in the Ru1212Eu sample,but  therefore, may be only a coincidence. Distinct AFM and FM transitions may coexist in both Ru1212R and Ru1222R.

These two transitions, as has been argued in the case of Ru1222R,fel ; xue2  may be due to either a mesoscopic phase-separation or a multistage transition. The magnetic properties between $`T_M`$ and $`T_{AM}`$, however, will be different in these two scenarios: some parts of Ru1212R should be in superparamagnetic states during phase separation, but should stay in a long-range spin-order state during a multistage transition. Evidence for the possible phase-separation in Ru1222R, for example, is found in both the superparamagnetic $`M(H)`$ with a magnetic cluster-size of $`10^3`$ $`\mu `$B and the slow spin dynamics far above $`T_{FM}`$.xue2  Similar properties were therefore tested in the Cu-doped Ru1212Eu.

The Langevin function with an additional linear term, $`aH+m[c\mathrm{tanh}(\mu H/k_BT)k_BT/\mu H]`$, was used to fit the average magnetization in a $`M`$-$`H`$ loop (inset, Fig. 3a).xue2  The fit is reasonably good with the deduced $`\mu `$ between 100 and 700 $`\mu _B`$/cluster (closed symbols in Fig. 3a), which is 4–5 times smaller than those deduced in Ru1222R, but still far larger than that expected based on the spin-fluctuations. A cluster of 400 $`\mu _B200`$ Ru ions, for example, would be 4–5 nm or larger in an RuO layer. It should be further noted that the $`\mu `$ so-deduced may be only a lower limit of the actual cluster/spin-correlation length.all  The existence of such large clusters at $`T/T_M>1.1`$ will be difficult to be interpreted as a simple fluctuation. This deduced size, on the other hand, appears to be too small for a crystalline magnet, as is suggested in the multistage transition model.

The dynamic spin-response was also studied. The logarithmic increase of $`M_{ZFC}`$ at 5 Oe with time is almost unobservable, with the deduced rate of $`dlnM/dlnt<10^3`$ well within our experimental resolution, where 60 s $`<t<`$ 3600 s is the time after the field switch. This is rather different from that of Ru1222Eu,xue2  but in agreement with the unobservable relaxation of Ru1212R $`ac`$-susceptibility reported between 1 s and 100 s.ziv  The lack of relaxations under the above conditions is apparently related to the cluster size in Ru1212R (Fig. 3a), which is 4–5 times smaller and leads to a quicker equilibrium. The slow spin dynamics, therefore, should either be explored in a shorter time window or after an enhancement of the energy barriers. Several different experimental conditions were then tested, and significant nonlogarithmic relaxations were observed in the remnant magnetization after a 50 Oe field-cooling (Fig. 3b). It is interesting to note that the energy barriers are $`KV_c\mu H`$ and $`KV_c`$, respectively, for the $`M_{ZFC}`$ and the remnant magnetization, where $`K`$ and $`V_c`$ are the magnetic anisotropy and the coherent volume, respectively. This may make the remnant magnetization a more favorable candidate for investigating the slow dynamics. The strong $`T`$ dependence of the relaxation observed (Fig. 3b) suggests, in our opinion, that the relaxation observed is unlikely an artifact of the SQUID magnetometer, but supports the existence of superparamagnetic clusters.

As pointed out earlier, the phase-separation model may also offer a consistent interpretation for the conflicting NPD/NMR and superconductivity data reported previously.xue2  The conflict between the NPD and NMR data for the magnetic structure, for example, may be attributed to the fact that the two probes have different sensitivities to various magnetic species, like those well documented in manganites.kap  Similarly, the spatial separation between AFM and FM species offers a natural mechanism for the unusual superconductivity observed.xue  Superconductivity can coexist with the AFM matrix. The finely dispersed FM clusters, on the other hand, depress the local SC order parameter and serve as tunnel barriers for the Cooper pairs. The superconductivity, therefore, may retain a significant part of the condensation energy, but appears only as a Josephson-junction array. Similarly, the critical temperature observed in the transport will naturally be much lower than that associated with the corresponding $`C_p`$ anomaly,ber ; tal  and can be easily suppressed by external fields.lor  The intragrain penetration depth will also be much longer than those expected based on the proposed universal $`1/\lambda _2(T_c)`$.xue

In summary, a systematic separation between $`T_M`$ and $`T_{AM}`$ is observed in Ru1212Eu with Cu-doping, suggesting the coexistence of FM and AFM orders and the occurrence of a mesoscopic phase-separation in the compound. The superparamagnetic $`M(H)`$ as well as the slow spin-dynamics further support the interpretation.

###### Acknowledgements.

The work in Houston is supported in part by NSF Grant No. DMR-9804325, the T. L. L. Temple Foundation, the John J. and Rebecca Moores Endowment, and the State of Texas through the Texas Center for Superconductivity at the University of Houston; and at Lawrence Berkeley Laboratory by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering of the U.S. Department of Energy under Contract No. DE-AC03-76SF00098.


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# Transport and structural study of pressure induced magnetic states in Nd0.55Sr0.45MnO3 and Nd0.5Sr0.5MnO3

## I Introduction

In Nd1-xSrxMnO3 manganite, the size difference between Nd3+ and Sr2+ is large ($``$0.15 Å). With increasing Sr2+ concentration, the bandwidth increases. With changes in x, intriguing spin, charge, and orbital phases are produced and extensive studies have been performed on these systems.Tokura and Tomioka (1999)

In the x = 0.5 compound, on cooling from room temperature, a transition from a paramagnetic insulating (PMI) phase to a ferromagnetic metallic (FMM) phase occurs at $``$255 K and a transition from FMM phase to charge-ordered (CO) antiferromagnetic insulating (AFI) phase is observed at $``$155 K. The magnetic structure in the CO AFI phase is CE-type.Kawano et al. (1997) With the application of a magnetic field, the FMM state is enhanced and the charge-ordering state is suppressed completely above 7 T.Kuwahara et al. (1995) The magnetic field induced collapse of CO state is accompanied by a structural transition in which the volume increases drastically, leading to large positive magnetovolume effect.Mahendiran et al. (1999) Orbital ordering coincides with charge-ordering. Different orbital ordering types, $`d_{3x^2r^2}/d_{3y^2r^2}`$-typeNakamura et al. (1999) or $`d_{x^2y^2}`$-type,Zvyagin et al. (2002) have been suggested in this compound.

Nd0.45Sr0.55MnO3 is an A-type antiferromagnetic metal with coupled magnetic and structural transition at $``$225 K.Kawano et al. (1997) The Mn moments are ferromagnetically aligned in the ab-plane in Pbnm symmetry. Charge carriers are confined within the ab-plane while the transport along the c-axis is quenched, leading to highly anisotropic resistivity ($`\rho _c/\rho _{ab}`$$``$104 at 35 mK).Kuwahara et al. (1998) The antiferromagnetic spin ordering is accompanied by the $`d_{x^2y^2}`$-type orbital ordering, both of which are simultaneously destroyed by high magnetic fields, concomitant with a discontinuous decrease of resistivity.Hayashi et al. (2002)

In this manganite system, the magnetic, electronic and orbital transitions are correlated with an abrupt structural transition, in which the a and b lattice parameters are elongated and the c parameter is compressed (in Pbnm symmetry).Kuwahara et al. (1998) Other groups showed that in Nd0.5Sr0.5MnO3, during the transition from FMM to AFI CO state, the crystal symmetry is lowered to monoclinic P21/m.Eremenko et al. (2001); Laffez et al. (1996) Ritter et al.Ritter et al. (2000) suggested that the low temperature AFI CO phase is phase-segregated into two different crystallographic structures and three magnetic phases: orthorhombic (Imma) ferromagnetic, orthorhombic (Imma) A-type antiferromagnetic, and monoclinic (P21/m) charge-ordered CE-type antiferromagnetic phases, in which a magnetic field can induce the charge-ordered monoclinic phase to collapse and to transform into the FMM orthorhombic phase. Kajimoto et al.Kajimoto et al. (1999) showed that in the CE-type and A-type antiferromagnetic states, the MnO6 octahedra are apically compressed corresponding to $`d_{3x^2r^2}/d_{3y^2r^2}`$ or $`d_{x^2y^2}`$ orbital ordering.

Hydrostatic and uniaxial pressures affect the CO and FMM states differently. In Nd0.5Sr0.5MnO3, hydrostatic pressure ($`<`$$``$1 GPa) increases TC with dTC/dP = 6.8 K/GPa and decreases TCO at a rate of 8.4 K/GPa,Moritomo et al. (1997a) while uniaxial pressure along the c-axis decreases TC at a rate of 60 K/GPa and increases TCO at a rate of 190 K/GPa.hisa Arima and Nakamura (1999) In Nd0.45Sr0.55MnO3, with the application of uniaxial pressure along the c-axis, the A-type antiferromagnetic phase is stabilized by increasing TN at 66 K/GPa, implying the stabilization of the $`d_{x^2y^2}`$ orbital.hisa Arima and Nakamura (1999) In thin films, due to the effect of substrate, biaxial strain can be induced. In Nd0.5Sr0.5MnO3 thin films, the thickness dependent strain tunes the competition between CO insulating and FMM states,Prellier et al. (1999) and there are optimal strain conditions under which the CO or metallic states appear.Qian et al. (2001)

The correlation between the structure and the electronic and magnetic transitions indicates its crucial role in this doping system. We have studied the CO, FMM, and antiferromagnetic state changes in Nd0.55Sr0.45MnO3 and Nd0.5Sr0.5MnO3 through high-pressure (up to $``$6 GPa) resistivity and structure measurements. It is found that pressure induces similar electronic and magnetic behavior in them, which can be partially related to the changes of orthorhombic distortion under pressure.

## II Samples and Experimental Methods

The samples were prepared by solid-state reaction. Stoichiometric amounts of Nd2O3, MnO2, and SrCO3 powder were mixed, ground, and calcined at 900 ℃ for 15 hours. The sample was then cooled down to room temperature and reground and then calcined again at 1200 ℃ for 17 hours. The powder was then pressed into pellets. The pellets were sintered at 1500 ℃ for 12 hours, cooled down to 800 ℃ at a rate of 5 ℃/min, and then quickly cooled down to room temperature. The pellets were annealed at 1200 ℃ and cooled down slowly to room temperature at 1 ℃/min. The x-ray powder diffraction patterns show a single crystallographic phase for each sample. The magnetization and resistivity measurements are consistent with the results of other groups.Tokura and Tomioka (1999); Caignaert et al. (1996); Tomioka et al. (1997) The details of the high-pressure resistivity and high-pressure x-ray diffraction measurement methods and error analysis were described previously.Cui et al. (2003)

## III Results and Discussions

### III.1 Nd0.55Sr0.45MnO3

Nd0.55Sr0.45MnO3 is a double exchange compound, with a FMM to PMI transition at $``$280 K upon warming. Under pressure, the electron transport is modified in an interesting manner. Figure 1(a) shows the resistivity as a function of temperature and pressure. The most important feature is the insulating state arising at low temperature under pressure. With pressure increase, the insulating behavior dominates above $``$6 GPa. Consequently, the resistivity in the measured temperature range changes with pressure \[inset of Fig. 2(a)\]. Below $``$3.5 GPa, the resistivity in the PMI phase is reduced while in the FMM phase it is almost unchanged. Above $``$3.5 GPa, in both phases, resistivity increases rapidly with pressure. In the low-pressure range, the metal-insulator transition temperature TMI increases with pressure. Due to the limit of the instrument, TMI above 325 K in the range of $``$2-4 GPa cannot be determined. Above $``$4 GPa, the transition temperature decreases on pressure increase. Above $``$6 GPa, the insulating behavior dominates so that the transition temperature cannot be determined, although there is still a trace of metallic behavior. The change of transition temperature with pressure is plotted in Fig. 2(a). The third-order polynomial fit gives a critical pressure P\*$``$2.6 GPa, while the resistivity in paramagnetic phase (at $``$316 K) gives P\*$``$3.6 GPa \[inset of Fig. 2(a)\].

In this compound, the behavior of TMI and resistivity is similar to that found in La0.60Y0.07Ca0.33MnO3 (Ref. Cui et al., 2003) and Pr0.7Ca0.3MnO3.Cui and Tyson (2003) However, the mechanism by which the materials become insulating at high-pressures is different. In those two compounds, the materials become insulating through the suppression of the FMM state, displaying a decreasing TMI above critical pressure. In Nd0.55Sr0.45MnO3, the insulating state at high pressures has two origins: the suppression of the FMM state and the expansion of a low temperature insulating phase, which appears with pressure increase and finally dominates at high pressures. The enhancement of the insulating phase is the dominant contribution to the change in resistivity.

Abramovich et al.Abramovich et al. (2000) proposed a phase-separation model in which the AFI droplets lie in a conducting ferromagnetic host. In the phase-separation model, the behavior of the material becoming insulating can be understood as pressure induced percolation where the increasing pressure suppresses the FMM component and enhances AFI component above P\*.

It is noted that the transport behavior at high pressures where the compound becomes insulating is similar to that of Nd0.45Sr0.55MnO3 at ambient pressure.Kuwahara et al. (1999) When high magnetic field of 35 T is applied, the resistivity of the A-type antiferromagnetic metallic Nd0.45Sr0.55MnO3 becomes similar to that of Nd0.55Sr0.45MnO3, which is ascribed to the destruction of the A-type antiferromagnetic spin ordering and $`d_{x^2y^2}`$ orbital ordering.Hayashi et al. (2002) Considering the similarity between the resistivity of x = 0.45 compound under high-pressure and x = 0.55 at ambient pressureKuwahara et al. (1999) and that of x = 0.55 in high magnetic field,Hayashi et al. (2002) one might speculate that the state induced by pressure in x = 0.45 compound has a similar spin and orbital structure to Nd0.45Sr0.55MnO3.

With the high-pressure structural measurements, it is found that the lattice is compressed anisotropically by pressure. The varying rates of change of lattice parameters under pressure lead to further distortion of the unit cell. To describe the orthorhombic distortion, Meneghini et al.Meneghini et al. (2002) defined the ab-plane distortion ($`Os_{ab}=2\frac{ab}{a+b}`$) and c-axis distortion ($`O_c=2\frac{a+bc\sqrt{2}}{a+b+c\sqrt{2}}`$) (in Pbnm symmetry). When the lattice is cubic, both Osab and Oc are zero. Figure 3(a) shows that both distortions increase under pressure, indicating a more distorted structure from the cubic case.

The structure of Nd0.45Sr0.55MnO3 is O ($`ab<\frac{c}{\sqrt{2}}`$).Kajimoto et al. (1999) The corresponding orthorhombic distortion is $``$0 in the ab-plane and -2% along the c-axis (calculated with the data in Ref. Kajimoto et al., 1999), which corresponds to the $`d_{x^2y^2}`$-type orbital ordering and the A-type antiferromagnetic metal state. Under pressure, the orthorhombic distortion for both the c-axis and the ab-plane increase in Nd0.55Sr0.45MnO3, indicating that the high-pressure structure is more different from Nd0.45Sr0.55MnO3 than at ambient pressure. The ab-plane distortion increase of Nd0.55Sr0.45MnO3 under pressure implies that the orbital state is different from that of Nd0.45Sr0.55MnO3 at ambient pressure. However, the similarity between the resistivities (in both absolute value and shape) seems to suggest that pressure induces an A-type antiferromagnetic state in Nd0.55Sr0.45MnO3.

### III.2 Nd0.5Sr0.5MnO3

Figure 1(b) shows the resistivity of Nd0.5Sr0.5MnO3 under pressure. In the low temperature CO AFI phase, the resistivity is reduced by pressure. On the other hand, the insulating region extends to higher temperature so that the ferromagnetic metallic state is suppressed. If the temperature where insulating and metallic states cross (the resistivity minimum) is defined as CO transition temperature, TCO increases first with pressure and appears to decrease above $``$3.8 GPa \[Fig. 2(b)\]. At the same time, pressure affects the metal-insulator transition only slightly. With pressure increase, TMI increases below $``$3 GPa and drops above $``$3 GPa. The highest TMI is only $``$4 K higher than that at ambient pressure. In the measured pressure range, resistivity in the PMI phase is suppressed.

TCO increases with pressure below $``$3.8 GPa while TMI shows almost no change \[Fig. 2(b)\]. This is different from the result that hydrostatic pressure ($`<`$1 GPa) increases TC and decreases TCO reported by other authors in single crystals.Moritomo et al. (1997a) On the contrary, our results are consistent with the effects of uniaxial pressure along the c-axis.hisa Arima and Nakamura (1999) In Fig. 3(b), it is seen that the c-axis distortion increases while the ab-plane distortion decreases with pressure. Because the CO state corresponds to a higher orthorhombic distortion state,Kuwahara et al. (1995) possibly the pressure induced increase of c-axis distortion enhances the CO state. On the other hand, the decrease in the ab-plane distortion may enhance the electron hoping and lead to the resistivity decrease in the ab-plane.

Roy et al.Roy et al. (2001) reported that pressure above $``$1.5 GPa splits the coincident antiferromagnetic and charge-ordering transitions in which TCO increases while TN decreases. With the transitions decoupled, resistivity rises abruptly at the magnetic transition but not at the CO transition, implying that low temperature resistivity comes mostly from the CE-type antiferromagnetic state. We did not observe the TCO and TN splitting in a larger pressure range, possibility because our sample is polycrystalline. In this case, the grain size distribution and randomly distributed grain orientations may lead to the broader CO AFI transition in polycrystalline samplesCaignaert et al. (1996) than in single crystal.Kuwahara et al. (1995) However, the large suppression of resistivity indicates that the antiferromagnetic state, specifically the CE-type antiferromagnetic state, is suppressed, which is also consistent with the ab-plane orthorhombic distortion reduction \[Fig. 3(b)\].

In Nd0.5Sr0.5MnO3, by substituting Nd3+ with larger size La3+, the bandwidth is increased and hence the CO phase is suppressed and TC increases. With applied pressure, a transition from the CO CE-type AFI to the A-type AFI was suggested, in which resistivity is suppressed and TCO gradually increases with pressure.Moritomo et al. (1997b) This is consistent with our result in the parent compound Nd0.5Sr0.5MnO3 and at a much higher pressure. The smaller ab-plane distortion and larger c-axis distortion at high pressures may favor an A-type antiferromagnetic state and $`d_{x^2y^2}`$ orbital ordering as in the x = 0.55 compound. In the A-type AFI state, resistivity is decreased due to enhanced in-plane transfer integral by the reduction of in-plane distortion. In the phase-separation model,Ritter et al. (2000) the A-type antiferromagnetic phase is enhanced and the CO CE-type antiferromagnetic phase is suppressed concomitantly by pressure. Because the bandwidth is sensitive to the atomic structure of the MnO6 octahedra, especially the Mn-O-Mn bond angle, it is highly desired to measure the atomic structure to explain the electronic and magnetic behavior under pressure. Unfortunately, it has been found difficult to acquire the atomic structure information from x-ray diffraction, due to the large difference between the scattering factors of the Nd/Sr and oxygen atoms compared to the case of La0.6Y0.07Ca0.33MnO3 in our previous work,Cui et al. (2003) which makes the refinement to the oxygen coordinates in the unit cell extremely difficult. A similar case also exists in the study on the structure of PbO under high-pressure.Häussermann et al. (2001) So other experimental techniques, such as high-pressure Raman scattering, are proposed to probe the local structure changes under pressure.

The two Nd1-xSrxMnO3 manganites at x = 0.45 and 0.5 have very different electronic, magnetic, and orbital ground states at ambient conditions. However, when we compare the resistivity at high-pressure, we can find a surprising similarity between them \[Figs. 1(a) and 1(b)\]. Figure 4 is an example of the resistivity of these two compounds at pressures above the critical pressure. The similarity also seems to imply a similar electronic and magnetic state. The structural measurements partly justify this assumption. The orthorhombic distortion of x = 0.45 is increased by pressure to almost the same as that of the x = 0.5 compound at ambient pressure \[Figs. 3(a) and 3(b)\]. In addition, the similarity between the high-pressure resistivity of these two compounds and that of Nd0.45Sr0.55MnO3 also suggests an A-type AFI phase in the high-pressure phase.

It is interesting to compare the effects of pressure and strain in thin films. The inset of Fig. 4 shows the resistivity of Nd0.5Sr0.5MnO3 thin films of several typical thicknesses from Prellier et al.Prellier et al. (1999) With thickness decrease, the strain in thin films is found to increase.Qian et al. (2001) Compared with Nd0.55Sr0.45MnO3, the resistivity evolution with thickness decrease (strain increase) is in analogy to pressure increase in bulk Nd0.55Sr0.45MnO3, indicating that pressure increases strain in bulk sample proved by structure measurements.

## IV Summary

In summary, by studying the resistivity and structure of Nd1-xSrxMnO3 (x = 0.45, 0.5) at high pressures, it is found that they have a similar resistivity as a function of temperature, which results from the different effects of pressure on their structures. Under pressure, both the ferromagnetic metallic state in the x = 0.45 compound and the CE-type antiferromagnetic insulating state in the x = 0.5 compound are suppressed. By comparing the resistivity and structure with the x = 0.55 compound, pressure appears to induce a similar electronic and magnetic state in these two compounds with much different ground states. We suggest that the pressure induced magnetic states in both samples are A-type antiferromagnetic.

###### Acknowledgements.

The high-pressure x-ray diffraction measurements were performed at beamline X17B1, NSLS, Brookhaven National Laboratory which is supported by the U.S. Department of Energy under Contract No. DE-AC02-98CH10886. The authors would like to thank Dr. Jingzhu Hu at X17C, NSLS for her assistance on the pressure calibration for x-ray diffraction. This work is supported by the National Science Foundation under Grant No. DMR-0209243.


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# Evidence for orbital ordering in 𝐿𝑎𝐶𝑜𝑂₃

## Abstract

We present powder and single crystal X-ray diffraction data as evidence for a monoclinic distortion in the low spin ($`S=0`$) and intermediate spin state ($`S=1`$) of $`LaCoO_3`$. The alternation of short and long bonds in the *ab* plane indicates the presence of $`e_g`$ orbital ordering induced by a cooperative Jahn-Teller distortion. We observe an increase of the Jahn-Teller distortion with temperature in agreement with a thermally activated behavior of the $`Co^{3+}`$ ions from a low-spin ground state to an intermediate-spin excited state.

The study of orbital degrees of freedom in transition metal (TM) oxides has gained prominent interest. Novel techniques such as Resonant X-ray Scattering and X-Ray Absorption Spectroscopy give direct information about orbital occupancy. It is realized that the orbital moments are as important as the spin moments to understand the electronic properties. Prominent examples in which the orbital degrees of freedom determine the electronic properties are the metal-insulator transitions in $`V_2O_3`$ Paolasini  and doped $`LaMnO_3`$Murakami . Here, spin- and orbital-induced transitions are intimately related. In the perovkites, metallicity and orbital ordering are mutually exclusive because of the large Jahn-Teller (JT) splitting of the $`e_g`$ orbitals Aken . Furthermore, novel ground states can be obtained such as an orbital liquid Khaliullin ; Keimer .

Considerable interest in the perovskite-type $`LaCoO_3`$ originates from the puzzling nature of two transitions in this compound and the vicinity to a metal-insulator transition. The ground state of $`LaCoO_3`$ is a nonmagnetic insulator and there is no long range magnetic order at all temperatures. At low temperatures, the magnetic susceptibility increases exponentially with temperature exhibiting a maximum near 100K. At higher temperatures, a second anomaly is observed around 500K which is accompanied by a semiconductor to metal transition. The maximum at 100K was ascribed initially to a change of the spin state in the $`Co^{3+}`$ ions i.e. a transition from a low-spin (LS) nonmagnetic ground state ($`t_{2g}^6`$, $`S=0`$) to a high-spin (HS) state ($`t_{2g}^4e_g^2`$, $`S=2`$) Asai ; Itoh ; Yamaguchi ; Senaris . In the more recent literature Potze ; Saitoh ; Asai2 ; Yamaguchi2 ; Kobayashi , new scenarios involving an intermediate-spin state (IS) ($`t_{2g}^5e_g^1`$, $`S=1`$) have been proposed. Using LDA+U calculations, Korotin *et al.* Korotin  proposed the stabilization of the IS state due to the large hybridization between the Co-$`e_g`$ and O-$`2p`$ levels. Due to the partially filled $`e_g`$ level, the IS state is JT active. The degeneracy of the $`e_g`$ orbitals of $`Co^{3+}`$ ions in the LS state is expected to be lifted in the IS state by a JT distortion.

All structural studies, based on powder X-ray and neutron diffraction experiments are consistently interpreted in rhombohedral $`R\overline{3}c`$ symmetry and no structural transitions are reported in the temperature interval $`4.2K1248K`$ Thornton ; Kobayashi2 ; Radelli ; Louca . A cooperative JT distortion is incompatible with this space group. The rhombohedral distortion of the parent cubic perovskite structure consists of a deformation along the body diagonal, and preserves only one $`CoO`$ distance. This triggered our present study to detect a coherent JT distortion and to investigate why recent high quality structural studies failed to observe such state. As the JT distortion caused by $`e_g`$ orbital ordering are usually quite large, there must be reasons why the distortion went unobserved. Furthermore, the LS-IS transition is robust and observed both in powder and single crystal samples. A lattice distortion due to the JT effect in the IS state has been suggested by infrared spectroscopy measurements Yamaguchi2  and recently by magnetic susceptibility and thermal expansion measurements Zobel .

It is in certain cases exceedingly difficult to identify the correct crystal symmetry. In perovskites such as $`LaMnO_3`$ or $`YVO_3`$ the JT distortion involves alternating long and short TM-O distances without always lowering the symmetry of the lattice Blake . Consequently, refinement of powder diffraction data are not very sensitive to several symmetry modifications and single crystal diffraction is prerequisite to determine the crystal symmetry. $`LaCoO_3`$ has been consistently analyzed with the rhombohedral space group $`R\overline{3}c`$. This rhombohedral symmetry involves an alternating rotation of the corner sharing $`CoO_6`$ octahedra along all three crystallographic axes of the undistorted, cubic perovskite parent structure. The corner sharing oxygen octahedra can be described by one oxygen position. This symmetry allows only one $`CoO`$ distance and thus rules out a coherent JT distortion. Such distortion, while preserving the alternating rotation of the $`CoO_6`$ octahedra, lowers the symmetry to monoclinic subgroups of $`R\overline{3}c`$. The monoclinic space group $`I2/a`$ cell  is a subgroup of $`R\overline{3}c`$ with the highest symmetry that accommodates the rotations of the octahedra as well as a coherent JT distortion. The symmetry reduction to $`I2/a`$ space group is caused by rotations of unequal magnitude and/or a differentiation of $`CoO`$ bond lengths, induced by a coherent JT distortion. In this symmetry two oxygen positions describe the oxygen framework. A shift of the second oxygen position with $`x_{O2}=y_{O2}`$ corresponds with a differentiation of $`CoO`$ bond lengths, whereas a movement perpendicular to this constraint results in a coherent rotation of the octahedra.

We provide strong evidence for such monoclinic distortion in the LS/IS state using high resolution synchrotron single crystal and powder diffraction experiments. The monoclinic distortion is ascribed to a JT distortion that signals the long range ordering of the $`e_g`$ orbitals. Our results are in agreement with the LS/IS state scenario in which the occupation of the IS states of the $`Co^{3+}`$ ions is thermally activated from the ground LS state Zobel .

Single crystals of $`LaCoO_3`$ were grown by the floating-zone technique in an image furnace. High resolution X-ray diffraction measurements were performed on a triple-axis high energy diffractometer with a photon energy of 115 keV at the beamline 11ID-C, BESSRC CAT, Argonne National Laboratory. $`\omega \chi `$ scans were collected on a single crystal of approximate dimension 1mm. Full data sets were measured on a small single crystal fragment of approximate dimension 0.1mm using $`MoK_\alpha `$ radiation. The measurements were collected using a Bruker SMART CCD camera and face indexed absorption corrections were performed using associated software packegesSheldrick1 . The integration of the frames was carried out using the SAINT Sheldrick1  software incorporating the absorption correction program SADABS. The separation of the twins was done using the program GEMINI Sheldrick1 . Structural determination and refinement was carried out using the SHELXTL Sheldrick1  package.

We measured the temperature dependence of the magnetization of single crystal $`LaCoO_3`$. The magnetization can be fitted well with a non magnetic ground state ($`t_{2g}^5`$) and a thermally activated $`S=1`$ state ($`t_{2g}^5e_g^1`$) with an activation energy of $`\mathrm{\Delta }180K`$, as shown recently by Zobel *et al.* Zobel . The stoichiometry of the crystal can be derived from the very small Curie-term, indicating less than 1% $`S=1`$ impurities. The impurity contribution gives rise to the deep minimum at 35K in the magnetic susceptibility. The raising of this minimum in the powder samples is attributed to $`Co^{2+}`$ localized magnetic moments associated with the reconstruction of the surface Senaris . The volume of this surface is larger for powder samples than for single crystals. Our single crystal measurement show a minimum susceptibility which is $`2`$ times smaller than in the powder samples Asai2 .

A full structure determination has been made by single crystal X-ray diffraction. However the crystals are highly twinned as is common both for orthorhombic and rhombohedral perovskites. Twinning can complicate the symmetry determination considerably.

The rhombohedral perovskites are obtained by a compression of the parent cubic cell along one of the body diagonals. The twinning is a result of the four body diagonals of which only one unique axis is chosen. The twin law relates four twin fractions by $`90^{}`$ rotation about the cubic main axes. The diffraction pattern of our samples typically exhibited two or three rhombohedral twins. The twinning ”masks” the reflection conditions associated with the lowering of the symmetry from $`R\overline{3}c`$ to $`I2/a`$, especially the *c*-glide plane and the three-fold axis. First, the violation of the *c*-glide plane will give rise to extra reflections. However, these reflections are also generated by the rhombohedral twinning. Therefore, their presence cannot be used as evidence for monoclinic distortion. Second, while the disappearance of the three-fold symmetry doesn’t generate new reflections, the resulting twinning mimics $`R\overline{3}c`$ symmetry. A small monoclinic distortion can give rise to such pseudo-merohedral twinning, which can be easily overlooked in a standard analysis due to insufficient angular resolution. Therefore, high angular resolution single crystal X-ray diffraction experiments are needed to determine the symmetry.

We verified the presence of twinning by performing $`\omega \chi `$ scans with high angular resolution (0.01 degrees/step) using synchrotron radiation. Such scans measure a cross section of reciprocal space on the Ewald sphere perpendicular to the scattering vector. In this way we measure the fine structure of a Bragg peak caused by twinning. Fig. 1 shows such a profile of a (10 2 8) reflection indices  in an $`\omega \chi `$ scan measured at 60K. The two big spots which split by 0.15(1) degrees in $`\omega `$, correspond to two twins generated by lowering the symmetry from cubic to rhombohedral. Each of these rhombohedral twins shows a further splitting of about 0.04(1) degrees in $`\omega `$. This smaller splitting is best observed at 20K and 60K but also the measured rhombohedral peaks at 120K and room temperature show clear shoulders. We attribute this smaller splitting to the twinning caused by the decrease in symmetry from rhombohedral to monoclinic. The same type of profiles are observed for all the peaks we have measured on several crystals. Such splitting indicates a distortion from the rhombohedral unit cell parameters. The observed splitting indicates that the monoclinic symmetry is maintained in the temperature interval 20K - 300K.

After establishing the symmetry of the structure, the atomic positions can be determined from standard single crystal diffraction experiments. Full data sets were measured at different temperatures (90K, 120K, 140K, 160K, 200K, 250K and 295K) on a Bruker APEX diffractometer, using $`MoK_\alpha `$ radiation. The rhombohedral twinning was clearly observable and the twins were analyzed separately. However, the monoclinic twinning could not be observed on this diffractometer due to insufficient angular resolution. The presence of the monoclinic twins was observed on a Enraf-Nonius CAD4 diffractometer equipped with a point detector which yields a better angular resolution. Again, these measurements indicate the splitting of the rhombohedral peaks as evidence for monoclinic distortion. However, for structural refinement, the monoclinic twin fractions could not be separated. Therefore the unit cell parameters derived from the single crystal measurements are averaged at their rhombohedral values (Table 1). The intensities of the reflections were obtained from the largest rhombohedral twin fraction which includes the integrated intensity of the monoclinic twin fractions together. Nevertheless, precise positions of the atoms can be obtained by making use in the refinements of the monoclinic twin relation.

The pseudo-merohedral twinning in $`LaCoO_3`$ results from the loss of three-fold symmetry during the crystal growth or a structural phase transition at elevated temperature. Therefore, the twinning corresponds to the three possibilities of converting the rhombohedral axes in $`R\overline{3}c`$ symmetry into the *c*-axis in monoclinic symmetry. There is no physical reason for one twin to be favored over the others and equal volume fractions can be expected. All crystals that we investigated, exhibited such a monoclinic twinning. The twin law relates three twin fractions by $`120^{}`$ rotation about the cubic  direction. If the twin fractions are equal, the reflections (h,k,l) indices  and cyclic permutations have equal intensities and simulate the existence of a three-fold axis. Thus, it is not surprising that the quality of the refinements in both $`R\overline{3}c`$ and $`I2/a`$ space groups are essentially the same. However, by introducing this twin model, the quality of the refinements in $`I2/a`$ space group was improved , the resulting $`R1`$-values falling for a typical data set (140K) from 0.0445 to 0.0433. The refined values of the twin fractions ranges between 30% and 40%. The atomic coordinates for a typical data set (200K) and the selected bond lengths are displayed in Table II and Table III respectively.

Recent high resolution powder neutron diffraction measurements were analyzed with $`R\overline{3}c`$ symmetry and failed to identify a monoclinic distortion Radelli . We performed experiments on high quality powder obtained from a crushed single crystal using synchrotron radiation and high angular resolution: 0.001 degrees/step. We measured the temperature dependence of the profile of the (4 0 0) reflectionindices  as the degeneracy of this peak is expected to be lifted by lowering the symmetry from rhombohedral $`R\overline{3}c`$ space group to monoclinic $`I2/a`$ space group. The peak width is resolution limited ($`0.0025^{}`$) up to 65K and it starts to broaden gradually as the temperature is increased, reaching $`0.0036^{}`$ at 145K. We associate the broadening of the Bragg reflection with a gradual distortion of the structure. The monoclinic symmetry is compatible with a splitting of this reflection. In the left side of fig. 2 we show the temperature dependence of the splitting of the (4 0 0) reflection derived from the peak profiles. In the inset of fig. 2 we show the profiles of the peak at 45K and at 120K. The splitting in $`\omega `$ derived from the $`\omega \chi `$ scans on single crystals corresponds with a much smaller splitting in $`\theta 2\theta `$ scans in the Bragg geometry. Thus, due to limitation in angular resolution, the monoclinic distortion can go easily undetected in Bragg geometry powder X-ray diffraction.

We notice that powder and single crystal diffraction give complementary information. The single crystal analysis is of crucial importance for detecting the lowering of the symmetry. However, analyzing the single crystal data turns to be difficult due to pseudo-merohedral twinning and only yield proper crystallographic results when appropriate symmetry and twinning are used. No accurate lattice parameters can be derived from single crystal X-ray diffraction as they are averaged by the twinning. Nevertheless, the rotation and JT distortion can be accurately determined from a refinement. Once the correct space group is assigned, the lattice parameters can be more precisely determined from a powder X-ray diffraction measurement.

We derive three unequal Co-O bond lengths over the studied temperature range: one short, one long and one medium. The long and short Co-O distances correspond with the bonds in the *ab* plane, while the medium Co-O distances are the out of plane bonds. These results indicate a clear coherent Jahn-Teller effect associated with a Q2 type of distortion Kanamori . The right side of fig.2 shows the temperature dependence of the Jahn-Teller parameter, defined as the difference between the long and short bond lengths normalized by their average. The magnitude of the JT parameter increases with temperature, reaching $`6\%`$ at room temperature. This value is somewhat smaller than the JT distortion of $`10\%`$ found in $`LaMnO_3`$ at room temperature Rodriguez .

The distortion of the octahedra lifts the degeneracy of the $`e_g`$ orbitals and XAS data Hao  show that the $`z^2`$ \- like orbitals are thermally populated. The $`z^2`$ \- like orbitals have an antiferrodistortive ordering along all three directions suggesting a ferromagnetic coupling between magnetic sites Korotin . Such a ferromagnetic exchange interaction is also supported by polarized neutron measurements Asai . An antiferrodistortive orbital ordering giving rise to ferromagnetic interactions was also found in $`YTiO_3`$, where the $`t_{2g}`$ orbitals of $`Ti^{3+}`$ cations are occupied by a single electron Sawada . However, for this system the JT distortion involves $`t_{2g}`$ orbitals for which the magnitude of the distortion is roughly five times smaller than for $`e_g`$-based JT systems.

The discovery of a coherent JT distortion in $`LaCoO_3`$ offers novel insight and is unexpected considering the scrutiny with which this compound was studied. It is clear that the JT distortion may have gone unnoticed in single crystal X-ray diffraction experiments because of twinning. Moreover, the JT distortion is not easily detected by powder X-ray diffraction because of the very small monoclinic distortion.

Our measurements are in agreement with the recent magnetic and XAS measurementsZobel ; Hao , which were interpreted with a thermal activation of the IS spin state. Considering the fact that $`LaCoO_3`$ is close to a metallic ground state, the transition may involve more complex behavior. It is observed in the manganitesAken ; Mathur  that phases coexist of metallic and insulating states arises from a competition between JT-distorted and non-JT distorted regions in the sample. The propagation of strain in crystal may result in an appearance that closely resembles a transition. Such phase coexistence requires detailed real space measurements.

We conclude that $`LaCoO_3`$ exhibits a monoclinic distorted structure in the temperature interval 20K-300K. The monoclinic distortion state is brought about by a cooperative Jahn-Teller effect which triggers the long range orbital ordering of the $`e_g`$ orbitals. The gradual increasing with temperature of the Jahn-Teller distortion suggests the thermal population of the IS state of the $`Co^{3+}`$ ions.

We thank J.L. de Boer, M. Grüninger, A. Meetsma and L.H. Tjeng for stimulating discussions. This work is supported by the Netherlands Foundation for the Fundamental Research on Matter (FOM) and by the Deutsche Forschungsgemeinschaft through SFB 608. Use of the Advanced Photon Source was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. W-31-109-Eng-38.


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# Comments On ”Three Paradox of Quantum Information”

## I comments

When we say one state is a Entanglement-State,it means that the state can not be factorized to a product of only two states of subsytems.So when one want apply an operator on an entanglement state,he cannot only factorized the state but should calculate it directly.

As the paper,one can found that

$$H|0>=\frac{1}{\sqrt{2}}\{|0>+|1>\}$$

$$H|1>=\frac{1}{\sqrt{2}}\{|0>|1>\}$$

Then

$$H\frac{1}{\sqrt{2}}\{|0>+|1>\}=|0>$$

But $`\frac{1}{\sqrt{2}}\{|00>+|11>\}`$ don’t equal to $`\frac{1}{\sqrt{2}}\{|0>+|1>\}|\psi _2>`$,so when one applied H on the state $`|00>+|11>`$ for the first particle,it should be

$`H{\displaystyle \frac{1}{\sqrt{s}}}\{|00>+|11>\}={\displaystyle \frac{1}{\sqrt{2}}}\{(H|0>)|0>+(H|1>)|1>\}`$
$`={\displaystyle \frac{1}{2}}\{|00>+|10>+|01>|11>\}`$
Then applied H for the second particle,We got

$$H_1H_2\frac{1}{\sqrt{2}}\{|00>+|11>\}=\frac{1}{\sqrt{2}}\{|00>+|11>\}$$

and when follow this calculate,one would found there are no paradoxes.


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# Linear vs. nonlinear coupling effects in single- and multi-phonon atom-surface scattering

## Abstract

We present a comparative assessment of the features of inelastic atom-surface scattering spectra that are produced by several different forms of linear and nonlinear phonon coupling to the projectile atom. Starting from a simple theoretical model of atom-surface scattering and employing several recently developed exact numerical and approximate analytical methods we calculate and compare the scattering probabilities ensuing from each form of interaction and from each calculational scheme. This enables us to demonstrate that in the regime of thermal energy atom scattering from surfaces the dominant contributions to the zero-, one- and multi-phonon excitation probabilities obeying unitarity arise from linear coupling treated to all orders in the interaction.

Published in Phys. Rev. Lett. 90, 126103 (2003)

Theoretical interpretations of inelastic atom-surface scattering experiments carried out in the past two decades to investigate vibrational properties of the various surfaces have all been based on several assumptions concerning atom-surface interactions that have never been critically examined or discussed. The aim of the present Letter is to remedy this situation in one of its so far neglected aspects, viz. the lack of a detailed assessment of the effects that arise from different forms of atom coupling to quantized surface vibrations or phonons. We perform this task using a simple paradigmatic, yet realistic enough quantum model comprising all the essentials of single- and multi-phonon atom-surface scattering.

The first assumption adopted by the majority of the authors in the development of inelastic atom-surface scattering theories reviewed in Refs.  has been the linear coupling of scattered atoms to vibrational displacements of surface atoms (i.e. linear coupling to the phonon field), and only few authors have resorted to descriptions based on nonlinear coupling. The absence of a quantification of the effects originating from the different forms of coupling is rather surprising because they should manifest themselves in all the components of the scattering spectra, viz. in (a) elastic scattering probability given by the so-called Debye-Waller factor (DWF), (b) one-phonon scattering probability, and (c) multi-phonon scattering probabilities.

The second assumption concerns the treatment of one-phonon excitation probabilities. Here, a rather general consensus prevailed that these should be calculated in the limit of linear atom-phonon coupling and in the Born approximation using distorted waves accounting for reflections of the atom from the surface to all orders in the static atom-surface potential. However, as the distorted wave Born approximation (DWBA) yields non-unitary scattering amplitudes it can provide reliable estimates only for the relative magnitudes of single quantum excitation probabilities in the regime in which the multi-quantum excitations are negligible. In order to obtain accurate one-phonon excitation probabilities for comparison with the zero- and multi-quantum ones (which are all sensitive to the form of atom-phonon coupling) and with the experimental data, the DWBA results should be unitarised to comply with the optical theorem.

The most striking differences arising from the assumptions of either linear or nonlinear atom-phonon coupling are expected in the calculated multiphonon scattering probabilities. Recent He atom scattering (HAS) experiments have successfully revealed and disentangled the one- and multi-quantum features in the atom-surface scattering spectra for phonons with Einstein and acoustic type of dispersion. Hence, the resolution of the origin of multiquantum features in the measured spectra as being due either to (i) multiple single phonon scattering events describable in terms of linear coupling, or (ii) multiquantum excitations that arise from nonlinear coupling in each order of perturbation expansion, emerges as a task of utmost interpretative importance.

One of the important conditions for a conclusive testing of the roles that linear and nonlinear coupling may play in the various theoretical descriptions of atom scattering from surface phonons is that they all ought to be applicable to a model which realistically describes the essentials of a particular scattering system. Another condition is that a clear disentanglement of the single- and multi-quantum features is possible for comparison of the results of different theories with the available experimental evidence. Experimental systems that enable the easiest identification of and distinction between the various one- and multi-phonon excitations in atom-surface collisions are those in which atoms are inelastically scattered by dispersionless or Einstein phonons. In this case the inelastic scattering spectra display a series of well separated equidistant peaks at the multiples of Einstein phonon energy $`\pm \mathrm{}\omega _0`$ away from the elastic line. The weight of the $`n`$-th peak measures the probability of excitation of $`n`$ phonons in the course of scattering. A prototype collision system of this kind is provided by HAS from monolayers of Xe atoms adsorbed on Cu(111) and Cu(001) surfaces which support vertically polarized Einstein modes. Other systems with similar properties have also been reported in the literature. The model Hamiltonians required for a full quantum mechanical description of these systems have been presented elsewhere. However, for the present purpose all the relevant features of collision dynamics are included in the effective one-dimensional Hamiltonian $`H`$ that describes motion of a projectile nonlinearly coupled to a surface oscillator of frequency $`\omega _0`$. Denoting by $`z`$ $`(Z)`$, $`p`$ $`(P)`$ and $`m`$ $`(M)`$ the coordinate, momentum and mass of the scattered particle (surface oscillator), respectively, we can write

$`H`$ $`=`$ $`{\displaystyle \frac{p^2}{2m}}+{\displaystyle \frac{P^2}{2M}}+{\displaystyle \frac{M\omega _0^2Z^2}{2}}+De^{\alpha (zZ)}`$ (1)
$`=`$ $`{\displaystyle \frac{p^2}{2m}}+De^{\alpha z}+{\displaystyle \frac{P^2}{2M}}+{\displaystyle \frac{M\omega _0^2Z^2}{2}}+De^{\alpha z}(e^{\alpha Z}1)`$ (2)
$`=`$ $`H_0^p(p,z)+H_0^{osc}(P,Z)+V(z,Z).`$ (3)
Here, the elastic particle motion in the model static surface potential of the Born-Mayer form, $`U(z)=De^{\alpha z}`$, is described by distorted waves that are eigenstates of the particle Hamiltonian $`H_0^p(p,z)=p^2/2m+U(z)`$. By introducing a purely repulsive $`U(z)`$ we avoid the occurrence of resonant scattering effects associated with the bound states of the surface potential well that are unimportant for the present study. The inelastic scattering is governed by the interaction potential

$`V(z,Z)`$ $`=`$ $`De^{\alpha z}(e^{\alpha Z}1)`$ (4)
$`=`$ $`Z\alpha De^{\alpha z}+{\displaystyle \frac{Z^2\alpha ^2}{2}}De^{\alpha z}+\mathrm{}`$ (5)
$`=`$ $`ZV_1(z)+Z^2V_2(z)+\mathrm{},`$ (6)
that contains powers of oscillator displacements $`Z`$ to all orders. The main merit of the thus defined model lies in its amenability to exact numerical and approximate analytical treatments in the calculations of single- and multi-phonon scattering probabilities. This enables us to consistently investigate as how the different forms of atom-phonon coupling affect the scattering spectra.

In this Letter the exact numerical treatments of elastic and inelastic atom scattering probabilities are carried out by employing the coupled channels method(CC) to solve the Schrödinger equation of particle motion perturbed by three types of interactions embodied in expression (6): the linear coupling term $`ZV_1(z)`$, the sum of linear and quadratic coupling terms $`ZV_1(z)+Z^2V_2(z)`$, and the full potential $`V(z,Z)`$. Tractable analytical solutions for the same model are obtained for the cases of linear coupling $`ZV_1(z)`$ treated to all orders within the distorted wave exponentiated Born approximation (EBA) formalism based on cumulant expansion, and for the full coupling $`V(z,Z)`$ treated in the DWBA as regards the particle motion. With the exception of the latter approximation, all other mentioned treatments yield unitary results in that the sum of all calculated scattering probabilities equals unity. Separate treatment of the sum of linear and quadratic coupling terms is particularly instructive because the quadratic term gives rise to both inelastic and elastic scattering processes, viz. the simultaneous two phonon excitations and elastic scattering by the static potential $`V_2(z)`$ renormalised by emission and reabsorption of a virtual phonon, an effect that is not present in linear coupling theories. These features are diagrammatically illustrated in Fig. 1 in which the virtual phonon excitation is represented by a closed phonon loop. Diagrammatic perturbation expansion in $`V(z,Z)`$ shows that nonlinear coupling to all orders gives rise to the appearance of arbitrary number of closed phonon loops in any single- or multi-phonon vertex. This leads to a Holstein type of renormalisation of inelastic particle scattering matrix elements by the factor $`\mathrm{exp}[(\alpha u_0)^2/2]`$ where $`u_0^2`$ is the mean square displacement of the oscillator.

The calculations have been carried out for the elastic scattering probability $`P_0`$, the one-phonon scattering probability $`P_1`$, and the two-phonon scattering probability $`P_2`$ for the types of couplings and within the theoretical approaches described above by using the parameters representative of He and Ne atom scattering from adsorbed Xe atoms. Figure 2 compares the behaviour of $`P_n`$ $`(n=0,1,2)`$ calculated for linear, linear and quadratic, and full nonlinear couplings as the functions of scattered particle incoming energy $`E_i`$, for He atom scattering from Xe atoms adsorbed on a cold Cu surface. The generalisation to finite surface temperatures is straightforward but does not bring in new effects concerning the various types of atom-phonon coupling.

The important message that can be deduced from the behaviour of elastic scattering probability $`P_0`$ or the Debye-Waller factor depicted in Fig. 2 is an excellent agreement between the results of exact CC calculations for the sum of linear and quadratic and full nonlinear coupling in the whole range of the projectile incoming energy. This means that the nonlinear coupling effects are described to a high degree of accuracy already by the sum of linear and quadratic coupling terms. The EBA formalism that is based on approximate treatment of linear coupling to all orders is also in excellent agreement with the exact numerical results.

Almost identical conclusions pertain to the behaviour of the one-phonon scattering probabilities $`P_1`$ in Fig. 2. As expected, the exact linear coupling result slightly deviates from the exact nonlinear coupling results as it does not pick up all the processes that are present when the nonlinear coupling terms are switched on. Here we also show the one-phonon scattering probability calculated in the DWBA applied to the full nonlinear coupling interaction $`V(z,Z)`$. For very low incoming energies near the one-phonon excitation threshold $`E_i=\mathrm{}\omega _0=2.7`$ meV, i.e. in the one-phonon scattering limit in which linear coupling yields the dominant contribution, the scattering probability calculated in the DWBA with full nonlinear coupling is in a good agreement with the other ones. However, with the increase of $`E_i`$ the deviations from the exact result soon become large and signify the break down of this approximation due to the nonunitary treatment of all the scattering events induced by $`V(z,Z)`$.

Very similar trends are observed in the behaviour of two-phonon scattering probabilities ($`P_2`$ in Fig. 2). Again, the EBA results are in a very good agreement with the exact ones and hence this formalism proves to be a very reliable approximate method for treating multiphonon scattering in the quantum regime. This property allows us to use the analytical form of the EBA scattering probabilities to demonstrate that the maxima of $`P_1(E_i)`$ and $`P_2(E_i)`$ appear approximately at the values of $`E_i`$ for which $`P_1=P_0`$ and $`P_2=P_1`$, respectively, and that $`P_1(E_i)`$ is largely given by $`P_1(E_i)=n(E_i)\mathrm{exp}[n(E_i)]`$ where $`n(E_i)=\mathrm{ln}P_0(E_i)`$ is the mean number of phonons excited in the scattering event.

Qualitatively very similar results are retrieved for Ne atom scattering treated in the same model (see Fig. 3). Likewise the case of He scattering, all the unitary treatments yield quantitatively similar results which follow the general trends present in Fig. 2. The only strong discrepancy between exact and approximate results appears for the scattering probability calculated in the DWBA with nonlinear coupling, that again completely fails to reproduce exact results. The centre and lower panels also demonstrate as how due to the larger projectile mass the maxima of all the unitary one-phonon and two- phonon scattering probabilities shift to lower $`E_i`$ than in the case of lighter He atoms. This is readily explained by the scaling properties of $`n(E_i)`$ which in the quasi-elastic limit of the EBA, here valid for $`E_i\stackrel{>}{}`$ 10 meV, is very accurately reproduced by the expression $`n(E_i)=8u_0^2mE_i/\mathrm{}^2`$ that is independent of both $`\alpha `$ and $`D`$. This causes exponentially faster attenuation of the Debye-Waller factor and all phonon excitation probabilities for larger projectile masses and fixed incoming energies.

The most striking feature of the results shown in Figs. 2 and 3 is a complete failure of the DWBA with full nonlinear coupling to describe the two-phonon scattering probabilities. In view of this and the earlier established excellent agreement between the measured and calculated EBA scattering probabilities for several prototype systems, the most important conclusion that can be drawn from Figs. 2 and 3 is that in inelastic low energy atom-surface scattering the main contribution to the two- and higher order phonon scattering probabilities comes from successive one-phonon scattering events and not from the processes of simultaneous multiple phonon excitations from a single interaction vertex that arise in nonlinear coupling models. This clearly demonstrates that unlike the case of inelastic neutron scattering from crystal lattices, the application of DWBA combined with nonlinear coupling to interpret the multi-phonon features in thermal energy atom scattering spectra leads to erroneous results and therefore should be avoided.

In the present case of a one-dimensional scattering model the CC-computations of the scattering probabilities are feasible for both the linear and nonlinear forms of coupling. Therefore, in such cases it is advantageous to immediately resort to the full nonlinear coupling in the CC-calculations. This ceases to be the case with the treatments of nonlinear coupling by other methods that yield scattering probabilities fulfilling the unitarity requirement. Hence, the finding that the EBA results are in a very good agreement with the exact ones becomes particularly important for the treatment of full three-dimensional scattering problems involving dispersive phonons for which the CC-calculations may not be feasible yet. In view of this, the present results affirm the EBA as a powerful tool for reliable interpretation of low energy atom scattering from surface phonons.

In summary, we have investigated the effects of different forms of linear and nonlinear atom-phonon couplings on inelastic atom-surface scattering. By comparing the results of several exact numerical and approximate analytical treatments of a simple model of atom scattering from surface vibrations we have demonstrated that in the regime of thermal energy atom scattering the linear coupling interaction treated to all orders gives a dominant contribution to the scattering probabilities.