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# Parallel and Perpendicular Lamellae on Corrugated Surfaces

## 1 Introduction

Numerous ways to control the orientation of ordered meso-phases have been extensively studied in recent years. As an example, we mention that lamellar block copolymers (BCP) confined between two flat and parallel surfaces have been shown to orient parallel or perpendicular to the surfaces, depending on the surface separation . Furthermore, chemically patterned surface can induce perpendicular or even tilted lamellae, if the chemical interaction is strong enough . Applying shear is yet another effective method in producing large well-aligned samples , but this method is difficult to implement in thin films. Another related situation can be found in liquid-crystals, where surface anchoring determines the direction of adjacent molecules and affects the bulk orientation and possible defects . This type of surface effect has been studied extensively in relation to the Fréedericksz transition and in twisted nematic liquid-crystal displays. Electric field can be very useful in aligning samples in which a large dielectric or conductivity contrast exists between the components . However, the use of electric field requires rather sophisticated experimental setups in order to avoid adverse effects of ion accumulation at electrodes, short-circuits due to dust particles, etc. .

Most of the studies mentioned above are restricted to films in contact with flat and smooth solid surfaces. Little attention has been paid to the role of surface roughness on film morphology and orientation, although it is clear that non-flat surface topography gives rise to defects (e.g. vacancies in the lamellar ordering) and affects the lamellae orientation. Quite recently, experiments carried out by Hashimoto and co-workers on lamellar BCP films  addressed the question of how surface roughness affects BCP film orientation. In their study it was shown that the degree of surface roughness controls the lamellar orientation, leading to situations where the BCP films orient themselves parallel or perpendicular to the surface. These experiments serve as a starting point of our theoretical investigation, where we restrict ourselves to lamellar multilayer systems in contact with one corrugated surface. The model is expressed in terms of the elastic energy of lamellar or smectic systems, and is described by only two elastic constants. Hence, although some system-specific details are missing, the results are not restricted to BCP films, but are more general and equally apply to a broad class of systems ranging from smectic liquid-crystals to lyotropic (oil/water/amphiphile) systems. The main difference between these systems is in the values of the system parameters: the lamellar periodicity, strength of surface interaction and elastic constants.

The elastic deformation energy of lamellar layers is studied separately for parallel and perpendicular orientations. It is shown that depending on the surface corrugation amplitude and periodicity, phase transitions can occur between the two orientations. Since real surfaces are never ideally flat, understanding and characterizing surface roughness can be of great importance in controlling orientation of lamellar phases. This orientation mechanism is complementary to the mechanisms mentioned above of electric fields, shear and chemical surface patterning. In Sections 2 and 3 we calculate the deviations of lamellae from their corresponding flat perpendicular and parallel states. The free energy of the parallel and perpendicular states are compared in Sec. 4, and a general discussion and comparison with previous works follows in Sec. 5.

## 2 Perpendicular Layers on Corrugated Surface

Consider a lamellar system confined by one topographically corrugated surface, as depicted in Fig. 1. Instead of considering a rough surface having a random and quenched topography, we assume that the surface is characterized by a typical corrugation with a single amplitude and wavelength. The difference between a true rough surface and a corrugated one is not expected to be very significant as long as the rough surface amplitude and wavelengths do not vary much about their average values. A further simplification is that the surface height $`h`$ (measured along the $`z`$-direction) is taken to depend only on the lateral $`x`$ direction, while it is translational invariant in the $`y`$ direction:

$`h(x)=R\mathrm{cos}(q_sx)+h_0,`$ (1)
where the average $`h_0=h(x)`$ is taken hereafter to be zero, $`h_0=0`$, $`R`$ is the corrugation amplitude and $`d_s2\pi /q_s`$ is the surface lateral periodicity.

So far we described the quenched corrugated surface geometry. Next we consider the energetics and structure of a lamellar phase in contact with such a surface. We start by examining the order-parameter corresponding to lamellae which are perpendicular to the average surface position:

$`\varphi _{}(𝐫)=\varphi _0\mathrm{cos}(q_0x+q_0u(x,z)),`$ (2)
where $`\varphi _0`$ is the amplitude of lamellar concentration variations, $`d_02\pi /q_0`$ is the bulk lamellar spacing, and $`u(x,z)`$ is a slowly-varying phase describing the deviation from flat lamellae, perpendicular to the surface and given by $`\varphi _0\mathrm{cos}(q_0x)`$.

The total free–energy $`F`$ of the lamellar stack in contact with one surface can be written as a sum of two terms, $`F=F_b+F_s`$, where $`F_s`$ is the surface energy and $`F_b`$ is the bulk lamellar contribution. In a lamellar system there are different energy costs associated with bending and compression of the layers. It can be shown that for a slowly varying phase $`u(x,z)`$, an expansion of the free energy $`F_b`$ to quadratic order in $`u`$ and its spatial derivatives, can be written in complete analogy with smectic phases of liquid crystals as:

$`F_b={\displaystyle \frac{1}{2}}{\displaystyle \left[K\left(u_{zz}\right)^2+B\left(u_x\right)^2\right]dV}.`$ (3)
In the above equation the integral is over the entire volume, $`B`$ is the compression modulus and $`K`$ is the bending modulus. In BCP systems the model holds well in intermediate and strong segregations, where the two copolymer blocks are well separated in different domains and the chains are highly stretched. The elastic moudlii are $`Kd_0\gamma _{\mathrm{AB}}`$ and $`B\gamma _{\mathrm{AB}}/d_0`$, where $`\gamma _{\mathrm{AB}}`$ is the interfacial tension between the A and B polymer blocks, and $`d_0`$ is the lamellar periodicity . For typical di-BCP such as polystyrene/polymethylmethacrylate (PS/PMMA), where $`\gamma _{\mathrm{AB}}2`$ mN/m and $`d_050`$ nm, we estimate their values to be $`K10^{11}`$ J/m and $`B410^5`$ J/m3. For liquid crystals, $`K210^{11}`$ J/m and $`B10^7`$ J/m3 , whereas for lyotropic (water/surfactant/oil) systems, $`K`$ is about $`1k_BT/d_0310^{30}`$ J/m and $`B1`$ J/m3 . Clearly these lyotropic phases are very ‘soft’ and their elastic modulii have small values.

The penetration length arising from Eq. (3) is

$`\lambda (K/B)^{1/2}.`$ (4)
In lamellar di-BCP this length is proportional to the lamellar spacing, $`\lambda d_050`$ nm. In lyotropic systems this distance is very small because of the reduced rigidity.

The second term in the free energy is the surface contribution. Similar to previous works , we assume a short–range surface field coupled linearly with the lamellar order–parameter at the surface.

$`F_s={\displaystyle \sigma \varphi dS}.`$ (5)
The parameter $`\sigma `$ is the surface field and the integral is taken over the entire corrugated surface. The value of $`\sigma `$ is taken to be a constant throughout the surface, describing a corrugated surface which is chemically homogeneous. A positive (negative) $`\sigma `$ favors adsorption of negative (positive) $`\varphi `$ at the surface. In the language of an A/B di-BCP, this means that B (or A) monomers are preferentially adsorbed on the surface for $`\sigma >0`$ ($`\sigma <0`$). Assuming small distortions in the order parameter close to the surface, $`F_s`$ can be expanded to first order in $`u`$

$`F_s\sigma \varphi _0{\displaystyle \left[\mathrm{cos}(q_0x)q_0u\mathrm{sin}(q_0x)\right]dS}`$ (6)
The entire profile $`\varphi (x,z)`$ can now be calculated by using a variational principle on the bulk free–energy, Eq. (3). In terms of the phase $`u(x,z)`$, the resulting Euler-Lagrange differential equation away from the corrugated surface is,

$`\lambda ^2u_{zzzz}u_{xx}=0`$ (7)
This variation has to be complemented by a set of rather complex boundary conditions. They are obtained by taking the variation of the full $`F_b+F_s`$ on the corrugated surface, $`z=h(x)`$, defined in Eq. (1),

$`{\displaystyle \frac{f_b}{u_{zz}}}`$ $`=`$ $`0`$ (8)
$`{\displaystyle \frac{f_s}{u}}+\left({\displaystyle \frac{f_b}{u}}{\displaystyle \frac{}{z}}{\displaystyle \frac{f_b}{u_{zz}}}\widehat{z}\right)\widehat{n}`$ $`=`$ $`0`$ (9)
The unit vector normal to the surface is defined as: $`\widehat{n}=(q_sR\mathrm{sin}q_sx,1)/\sqrt{(q_sR\mathrm{sin}q_sx)^2+1}`$, and $`f_b`$ and $`f_s`$ are the integrand of the volume and surface integrals, Eqs. (3) and (6), respectively.

In order to proceed we need to make some further simplifications. Solving the partial differential equation, Eq. (7), with the complex boundary condition, Eqs. (8)-(9) is an extremely difficult task. A further simplification is to assume that $`u(x,z)`$ is given by the single bulk mode $`q_0`$ in the $`x`$ direction, while it contains a sum over all possible Fourier modes in the $`z`$ direction:

$`u(x,z)=\mathrm{e}^{iq_0x}{\displaystyle \underset{k}{}}A_k\mathrm{e}^{ikz}+c.c.`$ (10)
This simple sinusoidal form of $`u`$ along the surface $`x`$ direction may not fully account for the incommensurability that exists between the lamellar and surface periodicities. Defects and vacancies in the lamellar ordering along the surface are not included either. Equations (7) and (10) lead to a selection of specific $`k`$ modes depending on the bulk mode $`q_0`$ and the penetration length $`\lambda `$:

$`k^4+\lambda ^2q_0^2=0`$ (11)
This equation has two different roots, $`k_\pm `$ (and their two complex conjugates)

$`k_\pm `$ $`=`$ $`\pm \left({\displaystyle \frac{q_0}{\lambda }}\right)^{1/2}\mathrm{e}^{\pm i\pi /4}`$ (12)
where $`\mathrm{exp}(i\pi /4)=(1+i)/\sqrt{2}`$ is the 4th root of unity in the complex plane. The first boundary condition, Eq. (8), implies that $`A_{k_+}=A_k_{}`$. Throughout this paper we assume $`q_sR<q_0R1`$ , whence it is valid to approximate $`\sqrt{(q_sR\mathrm{sin}q_sx)^2+1}1`$ and $`\mathrm{exp}(ikR\mathrm{cos}(q_sx))1`$. The second boundary condition \[Eq.(9)\] then gives

$`\sigma \varphi _0q_0\mathrm{sin}q_0xiBq_sR\mathrm{sin}q_sx{\displaystyle \underset{k}{}}q_0A_k\mathrm{e}^{i(q_0x+kz)}iK{\displaystyle \underset{k}{}}k^3A_k\mathrm{e}^{i(q_0x+kz)}`$ $`=`$ $`0`$ (13)
The $`z`$-dependent term in the exponentials is neglected as can be justified for $`q_0R1`$. The second term (proportional to $`B`$) can also be neglected for $`q_sR1`$, leading to the final expression of the lamellar order parameter:

$`u`$ $`=`$ $`A_0\mathrm{e}^{i(q_0x+k{}_{+}{}^{}z)}+A_0\mathrm{e}^{i(q_0x+k{}_{}{}^{}z)}+c.c.`$ (14)
$`A_0`$ $`=`$ $`{\displaystyle \frac{\sigma \varphi _0q_0}{2K(k_+^3+k_{}^3)}}`$
where $`A_{q_0}`$ is denoted $`A_0`$ in order to simplify the notation. The full order-parameter expression is obtained by substituting $`u`$ from above in Eq. (2). The decay length of lamellar undulations is proportional to the lamellar spacing, $`1/k_\pm (\lambda /q_0)^{1/2}d_0`$.

The perpendicular lamellar stack on a rough surface is shown in Fig. 2. In Fig. 2(a) the lamellar periodicity is half of the surface one. The surface is attractive to the component marked in dark shades, causing them to expand in its vicinity. Light lamellae are in turn contracted close to the surface; this behavior is seen in part 2(c) too, where the surface periodicity matches the bulk lamellar one. Clearly, the curvature of the lamellae adjusts to the surface one in order to achieve the best compromise between elastic deformation and surface coverage.

## 3 Parallel Layers on Corrugated Surface

We now turn to describe a parallel lamellar stack in contact with the same sinusoidally corrugated surface. Our derivation is related to previous treatments , but the boundary conditions are handled differently by introducing the same type of surface term in the free energy $`F_s`$, as in the previous section. The lamellae can be described along the same lines as for the perpendicular case but keeping in mind the important points where the stack orientation affects the free energy:

$`\varphi _{}(𝐫)=\varphi _0\mathrm{cos}(q_0z+q_0u(x,z))`$ (15)
The perfect parallel layers, $`\varphi _{}(𝐫)=\varphi _q\mathrm{cos}q_0z`$ are recovered far from the surface (where $`u=0`$). The bulk lamellar phase free-energy is obtained simply by interchanging the roles of $`x`$ and $`z`$ axes in the free energy of Eq. (3): $`xz`$

$`F_b={\displaystyle \frac{1}{2}}{\displaystyle \left[K\left(u_{xx}\right)^2+B\left(u_z\right)^2\right]dV}`$ (16)
As for the case of perpendicular lamellae, the surface energy, Eq. (5), can be expanded in small $`u`$ as follows

$`F_s\sigma \varphi _0{\displaystyle \left[q_0u\mathrm{sin}(q_0z)\mathrm{cos}(q_0z)\right]dS}`$ (17)
The governing equation for $`u`$ is obtained from a variation principle applied to Eq. (16), $`\delta F_b/\delta u=0`$

$`\lambda ^2u_{xxxx}u_{zz}`$ $`=`$ $`0`$ (18)
with the boundary condition obtained from a variation of $`F_b+F_s`$ on the $`z=h(x)`$ corrugated surface.

$`{\displaystyle \frac{f_s}{u}}+\left({\displaystyle \frac{f}{u}}{\displaystyle \frac{}{x}}{\displaystyle \frac{f}{u_{xx}}}\widehat{x}\right)\widehat{n}`$ $`=`$ $`0`$ (19)
Writing $`u`$ as $`u(x,z)=A_0\mathrm{e}^{i\alpha z}\mathrm{cos}q_sx`$ and using Eq. (18) we find that $`\alpha =i\lambda q_s^2`$. At this point it should be emphasized that when the surface periodicity is larger than the lamellar periodicity ($`q_s<q_0`$), the decay length $`1/\alpha q_0/q_s^2`$ for the parallel stack is much larger than the decay length $`1/k_\pm 1/q_0`$ in the perpendicular case. This, in turn, means that for fixed $`R`$ the elastic deformation gives preference to perpendicular ordering.

As in the case of perpendicular lamellae, we use $`q_sR<q_0R1`$ to approximate
$`\sqrt{(q_sR\mathrm{sin}q_sx)^2+1}1`$ and obtain from the boundary condition, Eq. (19),

$`\sigma \varphi _0q_0^2R+B\lambda q_s^2A_0=0`$ (20)
yielding the order-parameter of parallel lamellae

$`u(x,z)`$ $`=`$ $`A_0\mathrm{e}^{i\alpha z}\mathrm{cos}q_sx`$ (21)
$`A_0`$ $`=`$ $`{\displaystyle \frac{\sigma \varphi _0q_0^2R}{B\lambda q_s^2}}=R{\displaystyle \frac{\sigma \varphi _0}{\sqrt{BK}}}\left({\displaystyle \frac{q_0}{q_s}}\right)^2`$
The parallel layering given by Eq. (21) is plotted in Fig. 3. In 3(a) \[as in Fig. 2(a)\] the surface periodicity is twice larger than the lamellar one, and in 3(b) the two periodicities are equal. In the former case, dark regions (negative $`\varphi `$) appear close to the wall, the lamellae are able to closely follow the surface contour and distortions are long-range. In the latter case the surface topography changes too quickly for the lamellae to follow and the lamellae lie almost perfectly flat. Distortions of the stack, in this case, can be seen only in the very close vicinity of the surface.

## 4 Phase Diagram

The elastic energy of the lamellar phase in the two orientations is obtained by substitution of Eq. (14) in Eqs. (3) and (5) (perpendicular lamellae) and Eq. (21) in Eqs. (16) and (5) (parallel lamellae). Depending on the system parameters $`R`$, $`q_s`$, $`q_0`$ and $`\sigma `$, the minimum of the free energy is obtained for either one of the two orientations.

Before we proceed in presenting the corresponding phase diagram, we note that our derivation is not valid over the entire $`R`$, $`q_s`$, $`q_0`$ and $`\sigma `$ parameter space. The assumption of small distortions, $`q_0u1`$, together with Eq. (21) implies that $`R\sigma \varphi _0q_0^3q_s^2\sqrt{BK}`$. This can be rewritten as $`q_sR(q_0R)^{3/2}(\sigma \varphi _0/\sqrt{BK})^{1/2}`$. Combining these two inequalities, we obtain that the limits of validity of our derivation are given by

$`1q_0R>q_sR(q_0R)^{3/2}\left({\displaystyle \frac{\sigma \varphi _0}{\sqrt{BK}}}\right)^{1/2}`$ (22)
Cast in different terms this can be written as

$`\left({\displaystyle \frac{\sigma \varphi _0}{\sqrt{BK}}}\right)^{1/2}(q_0R)^{1/2}{\displaystyle \frac{q_s}{q_0}}<1`$ (23)
Before presenting the calculated phase diagram, it is of use to present a rough estimation of the parallel and perpendicular free–energies. Disregarding numerical prefactors, the bulk free energy of the perpendicular state is

$`{\displaystyle \frac{F_{}}{S}}`$ $``$ $`A_0^2\left(Bq_0^2+Kk_\pm ^4\right){\displaystyle \frac{1}{\mathrm{Im}(k_\pm )}}`$ (24)
$`=`$ $`{\displaystyle \frac{\sigma ^2\varphi _0^2}{K}}{\displaystyle \frac{1}{q_0}}`$
where $`S`$ is the surface area and $`A_0`$ is taken from Eq. (14). At distances from the surface greater than $`1/\mathrm{Im}(k_\pm )`$, the distortion $`u`$ is negligible, and the factor $`1/\mathrm{Im}(k_\pm )`$ represents the effective volume to area ratio of the integration.

The free energy of the parallel state is similarly estimated to be

$`{\displaystyle \frac{F_{}}{S}}`$ $``$ $`A_0^2\left(B\alpha ^2+Kq_s^4\right){\displaystyle \frac{1}{\mathrm{Im}(\alpha )}}`$ (25)
$`=`$ $`{\displaystyle \frac{\sigma ^2\varphi _0^2}{K}}{\displaystyle \frac{1}{q_0}}\left({\displaystyle \frac{q_0}{q_s}}\right)^2\left(q_0R\right)^2`$
Here $`A_0`$ is taken from Eq. (21) and the effective volume to area ratio is $`1/\mathrm{Im}(\alpha )`$.

The difference between the two free energies is roughly proportional to

$$F_{}F_{}\left(\frac{q_0}{q_s}\right)^2\left(q_0R\right)^21$$
(26)
Eq. (26) describes qualitatively the system behavior. If $`q_0`$ is fixed while $`R`$ and $`q_s`$ can vary, it directly follows that for $`q_0R>q_s/q_0`$ the perpendicular state is favored, while for $`q_0R<q_s/q_0`$ the parallel state is favored. Similar relations hold when $`q_s`$ is fixed and $`R`$ and $`q_0`$ are allowed to vary, or when $`R`$ is fixed but $`q_s`$ and $`q_0`$ can vary.

The above simplified approach describes qualitatively the system behavior and may be used as a ‘rule of thumb’. Furthermore, the surface energies and the correct numerical prefactors can be taken into account as well. Figure 4 shows the phase diagram in the ($`q_s,R`$) plane, for fixed $`q_0`$ and $`\sigma `$. Not the entire shown phase diagram is within the range of validity discussed above, Eq. (23). For small values of $`q_s`$, the perpendicular layering is favored, because of the long-ranged elastic strain pertaining in parallel lamellae as compared to perpendicular ones. As $`q_s`$ increases, the strain in the parallel state becomes more restricted to the vicinity of the surface, until, eventually, the parallel state becomes more stable. At this transition point, the energetic gain of having a commensurate layer close to the surface overcomes the loss of elastic energy deformation.

Different conclusion can be drawn for small values of surface amplitude $`R`$, which generally induce a parallel state. Keeping $`q_s`$ fixed and gradually increasing $`R`$ means that the elastic energy of deforming parallel lamellae increases, while the surface interaction stays constant. Therefore, at a certain threshold value of $`R`$ there is a transition from parallel to perpendicular ordering. For larger $`q_s`$ values this critical $`R`$ value increases as well.

Figure 5 is a phase diagram in the $`(R,q_0)`$ plane, with $`q_s`$ kept fixed. For a given BCP chain length (fixed $`q_0`$), increase of $`R`$ will also increase the elastic energy of deforming parallel lamellae, and promotes perpendicular layering. On the other hand, keeping $`R`$ fixed and decreasing $`q_0`$ (so that it becomes comparable to $`q_s`$) decreases the range of parallel deformation; thus, favoring the parallel state.

## 5 Discussion

Lamellar stacks of either liquid crystals (smectics), short chains amphiphiles or long-chain BCP undergo deformation as they try to adjust to the presence of a rough (corrugated) surface. The amplitude and spatial extent of inplane and out-of-plane deformations are different and the preference for parallel or perpendicular orientations depends on specific bulk and surface parameters. Which morphology prevails depends on the surface periodicity $`d_s=2\pi /q_s`$, surface amplitude $`R`$, lamellar periodicity $`d_0=2\pi /q_0`$, as well as the surface field strength $`\sigma `$.

For lamellae oriented perpendicular to the surface we use a model that indicates how the stack deformation propagates from the surface into the semi-infinite bulk. Parallel lamellae are studied using a modification of a model used previously for smectics phase. In both cases small surface corrugation is assumed such that we can use the limits: $`q_sR1`$, $`q_0R1`$. Our study is complementary to a numerical study by Podariu and Chakrabarti  who studied in detail extremely thin films (thickness comparable or smaller than the lamellar thickness) of a lamellar stack.

The system behavior in terms of the parameters $`R`$ and $`q_s`$ is given in the phase diagram of Fig. 4. For fixed surface periodicity $`2\pi /q_s`$, increase in the surface amplitude $`R`$ leads to preference of perpendicular lamellae. On the other hand, keeping $`R`$ fixed and increasing $`q_s`$ leads to preference of parallel lamellae. This is a consequence of the diminished decay length of surface-induced undulations. When the undulations of parallel lamellae are restricted to the surface vicinity, the energy penalty of the elastic defect can be small. Thus, the phase transition between these two states is described by a line in the two-dimensional phase diagram. Quite generally, as the surface interaction parameter $`\sigma `$ is increased, this line moves towards the $`R`$ axis in such a way that the state of parallel lamellae occupies a larger region in the phase diagram.

The transition from parallel to perpendicular orientation as function of $`R`$ and $`q_0`$ is given in Fig. 5. Increase of $`R`$ deforms the parallel layers and generally promotes perpendicular ordering. On the other hand, increase of $`q_0`$ while keeping $`R`$ and $`q_s`$ fixed, implies a reduced range of parallel deformations and yield a preference for parallel lamellae.

Rough surface can be used to obtain morphologies that are usually controlled by chemical means: not only the transition between parallel and perpendicular lamellae, but also tilted lamellar morphologies. Indeed, in the limit of very small lamellar periodicity (large $`q_0`$) and strong interfacial interactions $`\sigma `$, lamellae will appear locally perpendicular to the surface, and therefore tilt when the surface is not horizontal. Similar tilted lamellae have been predicted for a BCP melt confined by chemically patterned surfaces , as the system tries to match the lamellae with the stripes.

The present work is motivated by and is of direct relevance to recent experiments of Hashimoto and co-workers on PS/PMMA symmetric di-BCP on rough surfaces . In the experiments, perpendicular orientation was observed for system parameters estimated to be $`q_s0.04`$ nm-1, $`q_00.33`$ nm-1 and $`R7.5`$ nm. This set of data is in complete accord with the scaling formula, Eq. (26), because $`q_0^4R^2/q_s^21`$ is large and positive. This also can be confirmed by the phase diagrams presented in Figs. 4 and 5.

For different surfaces and BCP films reported in Ref. , $`q_s0.018`$ nm-1, $`q_00.19`$ nm-1 and $`R2.7`$ nm, and the film orients itself in parallel layers. The scaling formula, Eq. (26) yields here a small positive number, implying weak preference for perpendicular layers. The phase diagram also show marginal behavior, possibly preferential for perpendicular layers. This discrepancy can have several (yet unknown) origins. First, the exact value of the surface interaction parameter $`\sigma `$ is not known from experiments, and it may be different than the values chosen by us in Figs. 4 and 5. Furthermore, we employed several approximations in our calculations ignoring, for example, possible vacancies in the perpendicular lamellae and the temperature dependence of the elastic modulii. We also assumed that the system is semi-infinite in the $`z`$-direction, while in experiments the BCP film thickness is finite. It may be that the BCP/air free surface can induce islands or other types of surface-induced defects that alter the simple picture employed by us. The free–energy model holds for BCPs in intermediate and strong segregations, but is less adequate for weaker segregations, as is possibly the case in the experiments. Lastly, our theory can be improved by taking into account more realistic surface roughness, instead of a single surface $`q`$-mode.

We hope that additional and detailed experiments of lamellar systems in contact with well characterized rough surfaces will shed more light on this problem, and will further motivate theoretical studies of these intriguing systems.

Acknowledgements.  We thank T. Hashimoto and E. Sivaniah for many discussions and correspondence, and for sharing with us their experimental results prior to publication. We thank M. Cloitre, J.-B. Fournier, F. Tournilhac and L. Leibler for useful discussions and comments. DA wishes to acknowledge support from the Israel Science Foundation under grant no. 210/02, and the Alexander von Humboldt Foundation, while YT thanks the Chateaubriand fellowship program.


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# BCS-like Bogoliubov Quasiparticles in High-Tc Superconductors Observed by Angle-Resolved Photoemission Spectroscopy

## Abstract

We performed high-resolution angle-resolved photoemission spectroscopy on triple-layered high-Tc cuprate Bi2Sr2Ca2Cu3O10+δ. We have observed the full energy dispersion (electron and hole branches) of Bogoliubov quasiparticles and determined the coherence factors above and below EF as a function of momentum from the spectral intensity as well as from the energy dispersion based on BCS theory. The good quantitative agreement between the experiment and the theoretical prediction suggests the basic validity of BCS formalism in describing the superconducting state of cuprates.

It is well known that BCS (Bardeen, Cooper, and Schrieffer) theory  explains many of fundamental thermodynamic, transport and magnetic properties of superconductors by introducing a simple picture that two electrons with opposite momenta and spins near the Fermi surface form a pair (Cooper pair) in the superconducting state. In the language of Fermi liquids , the quasiparticles (QPs) of the Cooper pairs are called Bogoliubov quasiparticles (BQPs)  which are defined as excitation of a single electron “dressed” with an attractive interaction between paired electrons. The BQPs play an essential role in characterizing the superconducting state via quantities such as the superconducting gap and its symmetry. Despite the excellent description of the BQPs in BCS theory, there has been no direct experimental observation of the predicted full energy dispersion (electron and hole branches) of BQPs, although the pairing of electrons is evidenced by ac Josephson-junction experiment . For high-Tc cuprates, the direct observation of the BQPs is even more significant, since many microscopic ideas of BCS theory have been seriously challenged. Since the BQPs are a natural consequence of the starting Hamiltonian including the two-body attractive interaction assumed by BCS theory , the existence of BQPs would prove the validity of the basic BCS description of the superconducting state in the cuprates.

In this Letter, we report the direct observation of BQPs in triple-layered high-Tc cuprate Bi2Sr2Ca2Cu3O10+δ by angle-resolved photoemission spectroscopy (ARPES). By using ultrahigh resolution in energy and momentum, we have succeeded in directly observing the full energy dispersion (electron and hole branches) of BQPs below and above the Fermi level (EF). We have determined experimentally the coherence factors as a function of momentum from ARPES intensity and compared the result with the prediction from BCS theory to investigate the basic validity of the theory in high-Tc cuprates.

High-quality single crystals of Bi2Sr2Ca2Cu3O10+δ (Bi2223, overdoped, Tc=108 K) were grown by the traveling solvent floating zone method . ARPES measurements were performed using a GAMMADATA-SCIENTA SES-200 spectrometer with 22 eV photons at the undulator 4m-NIM beamline at Synchrotron Radiation Center in Wisconsin. The energy and angular (momentum) resolutions were set at 11 meV and 0.2 (0.007Å-1), respectively. A clean fresh surface of sample was obtained by in-situ cleaving along the (001) plane. The Fermi level (EF) of the sample was referenced to that of a gold film evaporated onto the sample substrate.

Figure 1 shows a schematic comparison of spectra between the superconducting BQPs and the normal-state QPs. In the normal state \[Fig. 1(a)\], one-electron like QPs disperse across EF with an equal spectral weight, defining the Fermi vector (kF) at EF. In the superconducting state \[Fig. 1(b)\], the BQPs split the single band into two dispersing branches below and above EF. The BQPs exhibit several characteristic features: (i) the dispersion of two branches is symmetric with respect to EF; (ii) the minimum separation at kF defines the superconducting energy gap (2$`\mathrm{\Delta }`$); (iii) both the dispersions below and above EF show bending-back behavior at kF due to the particle-hole mixing; (iv) the spectral weight of the two branches differs, and changes with the wave vector k; however, (v) the combining weight of the two branches is always constant at any $`k`$.

Figures 2(a) and 2(b) show the ARPES spectra of Bi2223 in the normal and superconducting states, respectively, measured along the direction in the Brillouin zone shown in the inset in Fig. 2(e). We have surveyed many areas in the Brillouin zone and confirmed that the intensity of Umklapp bands is very weak and they do not contaminate the main-band dispersion in this momentum region. While we see a broad peak dispersing across EF in the normal state, we clearly observe a sharp coherent peak in the superconducting state. As k is changed from ($`\pi `$, 0) to (3$`\pi `$/2, -$`\pi `$/2), the coherent peak gradually disperses toward EF, showing a minimum energy gap at kF \[dark red line in Fig. 2(b)\], and then disperses back to the higher binding energy while rapidly reducing its intensity. These behaviors are consistent with the band dispersion below EF shown in Fig. 1(b) as well as with a previous ARPES result on Bi2Sr2CaCu2O8+δ (Bi2212) . More importantly, we find additional weak but discernible structures about 20 meV above EF in the spectra, which are more clearly seen in Fig. 2(c). This new structure shows a clear momentum dependence with a stronger intensity in the region of $`|k|>|k_F|`$, opposite to the behavior of the band below EF. We ascribe these small structures to the BQP band above EF by referring to Fig. 1(b) . The considerably weak intensity of the peaks above EF is simply due to the effect of the Fermi-Dirac (FD) function. In order to see more clearly the band dispersion above EF, we have divided the ARPES spectra by the FD function at 60 K convoluted with the instrumental resolution . The result is shown in Fig. 2(d), where we find a dispersive structure with comparable intensity above EF, although the signal-to-noise ratio is relatively low because of the originally small ARPES intensity. It is remarked here that dispite the low signal-to-noise ratio the bending-back behavior of band is also seen in the unoccupied states as in the occupied states. The dispersive feature is more clearly visualized in Fig. 2(e) by plotting the renormalized ARPES intensity as a function of momentum and energy. We observe several characteristic behaviors for the two branches: (i) the dispersive feature is almost symmetric with respect to EF while the intensity is not; (ii) the bands have a minimum energy gap at kF; (iii) both bands show the bending-back effect at kF; (iv) the spectral intensity of the two bands show opposite evolutions as a function of k in the vicinity of kF. All these features qualitatively agree with the behaviors of BQPs predicted from BCS theory \[Fig. 1(b)\], suggesting the basic validity of the BQP concept in high-Tc superconductors.

The next question is how quantitatively the observed dispersion and spectral weight agree or disagree with the predictions from BCS theory. This point is crucial in establishing the BQP concept more firmly in the cuprates. Figure 3(a) shows direct comparison between the experimental band dispersion of BQPs (same as Fig. 2(e)) and the corresponding calculated curves based on BCS theory. In BCS theory, the band dispersion of BQPs ($`E_k`$) is expressed as $`E_k=[ϵ_{k}^{}{}_{}{}^{2}+|\mathrm{\Delta }(k)|^2]^{1/2}`$, where $`ϵ_k`$ and $`\mathrm{\Delta }(k)`$ are the normal-state dispersion and the superconducting gap, respectively. We have determined at first $`ϵ_k`$ and $`\mathrm{\Delta }(k)`$ from the ARPES spectra at 140 and 60 K in Fig. 2, respectively, and then calculated the “theoretical” band dispersion of BQPs using the above equation. The normal state dispersion $`ϵ_k`$ \[white solid line in Fig. 3(a)\] is obtained from the peak position in ARPES spectra at 140 K \[white open circles in Fig. 3(a)\] by fitting them with parabolic function. The superconducting gap $`\mathrm{\Delta }(k)`$ is assumed to be the $`d_{x^2y^2}`$-wave superconducting order parameter $`\mathrm{\Delta }(k)=\mathrm{\Delta }_0|cos(k_x)cos(k_y)|/2`$, where $`\mathrm{\Delta }_0`$ is determined by the peak energy of the 60-K spectrum at kF. We find in Fig. 3(a) that the calculated dispersion well traces the strong-intensity areas of ARPES spectra, showing good agreement in the band dispersion between the experiment and the theory. To further confirm the agreement in the unoccupied states, we have fit the normalized ARPES spectra in Fig. 2(d) with a Lorentzian and show the peak positions in Fig. 3(a). The peak positions are found to be well on the calculated curve, showing quantitatively good agreement between the experiment and the calculation.

To further study the validity of the BQP concept, we have determined the coherence factors above and below EF, $`|u_k|^2`$ and $`|v_k|^2`$, by using the following two independent methods and compared them with each other. The coherence factors are defined as the relative intensity of BQP bands above and below EF, which directly correspond to the normalized ARPES spectral intensity in the superconducting state. On the other hand, according to BCS theory, the coherence factors can be also calculated from the energy dispersions of the normal-state QP and the superconducting BQP bands in the following way:

$$|u_k|^2=1|v_k|^2=\frac{1}{2}(1+\frac{ϵ_k}{E_k})$$
(1)
where $`ϵ_k`$ and $`E_k`$ are the energy of the normal QP and BQP bands, respectively .

For the first method, we have determined $`|u_k|^2`$ and $`|v_k|^2`$ by fitting the original ARPES spectra in Fig. 2(b) by the following equation,

$`I(k,\omega )=`$ (2)
$`I_0(k){\displaystyle 𝑑\omega ^{}\{A_{BCS}(k,\omega ^{})+A_{inc}(k,\omega ^{})\}f(\omega ^{})R(\omega \omega ^{})}`$ (3)
where $`I_0(k)`$ is a prefactor which includes some kinematical factors and the dipole matrix-element. $`A_{BCS}(k,\omega )`$ is the BCS spectral function expressed as,

$$A_{BCS}(k,\omega )=\frac{1}{\pi }\{\frac{|u_k|^2\mathrm{\Gamma }}{(\omega E_k)^2+\mathrm{\Gamma }^2}+\frac{|v_k|^2\mathrm{\Gamma }}{(\omega +E_k)^2+\mathrm{\Gamma }^2}\}$$
(4)
where $`\mathrm{\Gamma }`$ is a linewidth broadening due to the finite lifetime of photoholes. $`A_{inc}(k,\omega )`$ in Eq. (2) is an empirical function representing the incoherent background , $`f(\omega )`$ is the FD function, and $`R(\omega )`$ is the Gaussian resolution function. To remove the effect of $`I_0(k)`$, we have divided the spectral intensity of the superconducting state (60 K) with the integrated normal-state (140 K) spectral intensity at each k point. We determine the peak weights below and above EF at each k point by decomposing the spectrum, and then divide them by the average value of the total peak weight at each k point . We define these normalized weights as $`|v_k|^2`$ and $`|u_k|^2`$ and show the results in Fig. 3(c). It is important to note here that $`|u_k|^2`$ and $`|v_k|^2`$ are determined independently without using the sum rule of $`|u_k|^2`$+$`|v_k|^2`$=1. The fittings have been performed within the momentum region where reliable values for the coherence factors can be obtained \[shown in Fig. 3(c)\], since the reliability of fitting is considerably decreased far above EF due to the low signal-to-noise ratio of the original ARPES spectra.

For the second method, we have calculated $`|u_k|^2`$ and $`|v_k|^2`$ by using Eq. (1) with $`ϵ_k`$ and $`E_k`$ obtained from Fig. 3(a). In Fig. 3(c), we show the comparison of the two sets of coherence factors determined by the ARPES intensity itself and by the BCS calculation based on the band dispersions, respectively. We find a surprisingly good quantitative agreement between the two sets of coherence factors determined totally independently . It is also remarked that the sum of coherence factors, $`|u_k|^2`$+$`|v_k|^2`$, determined by the ARPES intensity is almost constant over the measured momentum region, in good agreement with the sum rule of the coherence factors predicted from BCS theory.

The sharp superconducting quasiparticle peak at ($`\pi `$, 0) in Bi-based cuprates has been widely studied in the high-Tc field. The origin and its implications are still under debate. Some of its properties clearly deviate from BCS theory. For example, the leading edge of the quasiparticle peak does not reach EF even above Tc, indicating the opening of a pseudogap . Spectral weight of the quasiparticle peak increases with hole-doping and has an unusual temperature dependence . The present ARPES study, on the other hand, by its direct experimental observation of two dispersive branches with their dispersions and coherence factors consistent with the BCS predictions, has unambiguously established the Bogoliubov-quasiparticle nature of this sharp peak. This implies that the superconducting state of the high-Tc cuprate is BCS-like, so that some of the basic BCS formalism is still valid in this case, although the pairing mechanism and other exotic properties are beyond BCS theory. Thus this experimental observation provides a strong constraint in modeling the high-Tc problem. Moreover, this observation opens a new way to study quasiparticles in the superconducting state by probing the branch above EF populated by thermal or optical excitations. One particularly important application is to determine the nature of the gapped peak in the pseudogap state. This may potentially settle the debate between the precursor pairing gap and single-particle gap.

We thank T. Tohyama, K. Yamada, J. R. Engelbrecht and Z. Wang for useful discussions. This work is supported by grants from the MEXT of Japan, US NSF DMR-0072205, and Sloan Foundation. T.S. thanks JSPS for financial support. The Synchrotron Radiation Center is supported by US NSF DMR-0084402.

Present address: Department of Applied Physics, Waseda University, Tokyo 169-8555, Japan
Present address: NTT Photonics Laboratories, Atsugi 243-0198, Japan


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# Effect of band-filling and structural distortions on the Curie temperature of Fe-Mo double perovkites

## Abstract

By means of high resolution neutron powder diffraction at low temperature we have characterized the structural details of $`\mathrm{La}_\mathrm{x}\mathrm{Sr}_{2\mathrm{x}}\mathrm{FeMoO}_6`$ ($`0\mathrm{x}0.5`$) and $`\mathrm{Ca}_\mathrm{x}\mathrm{Sr}_{2\mathrm{x}}\mathrm{FeMoO}_6`$ ($`0\mathrm{x}0.6`$) series of compounds. This study reveals a similar variation of the mean bond-angle $`\theta _{\mathrm{Fe}\mathrm{O}\mathrm{Mo}}`$ in both series. In contrast, the mean bond-distance $`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$ increases with La but not with Ca substitution. Both series also present a different evolution of the Curie temperature ($`T_C`$), which raises in the La series and slightly decreases in the Ca one. We thus conclude that the enhancement of $`T_C`$ in the La series is due to the electron filling of the conduction band and a concomitant rising of the density of states at the Fermi level.

Double perovskites of the type $`\mathrm{A}_2\mathrm{FeMoO}_6`$ ($`\mathrm{A}=\mathrm{Sr}`$, Ba, Ca), have been predicted to be half-metallic ferromagnets up to their Curie temperature ($`T_C`$), well above room temperature.Kobayashi et al. (1998) This fact makes them very attractive from the point of view of applications in magnetoelectronics, and have lead to a growing interest in this and other families of double perovskites. In the ideal double perovskite structure Fe and Mo ions are perfectly ordered in the B position of the perovskite forming two interpenetrating cubic sublattices but, experimentally, this order is not perfect.Balcells et al. (2001) The low field magnetoresistance is substantial although it decreases as the temperature approaches $`T_C`$, so in order to enlarge the working range of the potential applications, the main goal of numerous studies has been to enhance the Curie temperature of these compounds. In the celebrated manganites, this objective was achieved by broadening the conduction band, that is, by enlarging the Mn-O-Mn bond angle via the appropriate introduction of large cations in the A-site position of the perovskite building block. Using this approach, an enhancement of $`T_C`$ of about $`100\mathrm{K}`$ has been obtained when substituting Ca by Sr in $`\mathrm{La}_{2/3}\mathrm{Ca}_{1/3\mathrm{x}}\mathrm{Sr}_\mathrm{x}\mathrm{MnO}_3`$. Interestingly enough, when the same strategy is used in the double perovskites, a very modest enhancement of $`T_C`$ of only $`20\mathrm{K}`$ has been obtained. Indeed, the Curie temperatures of $`\mathrm{Ca}_2\mathrm{FeMoO}_6`$ and $`\mathrm{Sr}_2\mathrm{FeMoO}_6`$ are of about $`380\mathrm{K}`$Alonso et al. (2000) and $`400\mathrm{K}`$Kobayashi et al. (1998); Balcells et al. (2001) respectively.

This streaking dissimilarity indicates substantial differences in the nature of the ferromagnetic (FM) coupling in these oxides and suggests that the origin of ferro- (or ferri-) magnetism in double perovskites is different from the double exchange mechanism governing FM manganites.Ray et al. (2001) It has been recently proposed that delocalized electrons, antiferromagnetically coupled to localized magnetic moments (Fe3+: $`3d^5`$), mediate the magnetic coupling, resulting in a net FM interaction between Fe ions. In fact, the magnetic properties, at high temperature (above $`T_C`$), of $`\mathrm{Sr}_2\mathrm{FeMoO}_6`$ can only be properly described if the contribution from delocalized electrons of the conduction band and its antiferromagnetic (AFM) interaction with localized spins are taken into account.Tovar et al. (2002) A direct consequence of this model is that the strength of the FM interaction is governed by (i) the strength of the AFM coupling between core spins and itinerant electrons and (ii) the density of electrons at the Fermi level \[$`D(E_F)`$\]. This in turn indicates that a possible way to modify and eventually enhance $`T_C`$, could be the filling of the conduction band with doping electron carriers. This approach has been proven to be successful and recently a substantial enhancement of $`T_C`$ by more than $`80\mathrm{K}`$ has been reported in $`\mathrm{Sr}_{2\mathrm{x}}\mathrm{La}_\mathrm{x}\mathrm{FeMoO}_6`$ and $`(\mathrm{Ba}_{0.8}\mathrm{Sr}_{0.2})_{2\mathrm{x}}\mathrm{La}_\mathrm{x}\mathrm{FeMoO}_6`$ series, where a divalent Sr ion is substituted by a trivalent La ion.Navarro et al. (2001); Serrate et al. (2002); Navarro et al. (In press) Spectroscopic photoemission measurements have been used to show that indeed $`D(E_F)`$ in $`\mathrm{Sr}_{2\mathrm{x}}\mathrm{La}_\mathrm{x}\mathrm{FeMoO}_6`$ enhances when $`\mathrm{x}`$ is augmented.Navarro et al. (2003) Although these experiments did provide a solid confirmation of the relevant role of the itinerant carriers in the FM coupling in double perovskites, they have not settled the microscopic origin of the observed rising of $`D(E_F)`$. The difficulty arises because in these doped materials, the La substitution not only may provide carriers to the conduction band but also shall promote a structural distortion owing to the different ionic radii of Sr2+ and La3+ ions. As a result of it, the observed enhancement of $`D(E_F)`$ cannot be exclusively attributed to a band-filling effect. In sharp contrast with experiments, theoretical analyses, assuming undistorted lattice, have predicted that $`T_C`$ may lower upon electron doping, in contrast with experiments.Alonso et al. (2002) Therefore, discrimination between these effects (steric and band-filling) is a critical issue for understanding the mechanism of FM coupling in double perovskites and for the design of semi-metallic materials having still higher $`T_C`$.

In order to solve this problem and to elucidate the origin of the $`T_C`$ enhancement we report here a detailed structural analysis of two complementary series of materials: La substituted and Ca substituted $`\mathrm{Sr}_2\mathrm{FeMoO}_6`$. We show that this selection of materials allows to discriminate between band-filling and structural distortion effects. From the comparison of the structural and magnetic data we conclusively show that band-filling effects dominate and are the responsible of the enhancement of the Curie temperature in La substituted compounds. In contrast, the structural distortions found in the Ca case (similar to those found in the La case) reduce $`T_C`$.

Ceramic samples of $`\mathrm{La}_{\mathrm{x}_{\mathrm{La}}}\mathrm{Sr}_{2\mathrm{x}_{\mathrm{La}}}\mathrm{FeMoO}_6`$ ($`0\mathrm{x}_{\mathrm{La}}0.5`$) and $`\mathrm{Ca}_{\mathrm{x}_{\mathrm{Ca}}}\mathrm{Sr}_{2\mathrm{x}_{\mathrm{Ca}}}\mathrm{FeMoO}_6`$ ($`0\mathrm{x}_{\mathrm{Ca}}0.6`$) have been synthesized by solid reaction in adequate atmosphere. Stoichiometric amounts of high purity ($`>99.99\%`$) $`\mathrm{Fe}_2\mathrm{O}_3`$, $`\mathrm{MoO}_3`$, $`\mathrm{SrCO}_3`$, $`\mathrm{CaCO}_3`$, and $`\mathrm{La}_2\mathrm{O}_3`$ have been mixed. After the initial prefiring treatments to decarbonate the compounds the powders have been pressed into rods. The final firing has been done at $`1250^\mathrm{o}\mathrm{C}`$ in Ar/H-1% (followed by slow cooling down). The quality of the compounds was initially checked by laboratory X-ray powder diffraction (XRPD), using long collecting times in order to obtain very good statistics. The obtained samples are well crystallized and single phased. Only small traces ($`0.8\%`$) of $`\mathrm{SrMoO}_4`$ have been detected in some patterns. XRPD data have been used to determine the concentration of antisites (AS), defined as the fraction of Fe (Mo) ions in the Mo (Fe) sublattice (thus $`\mathrm{AS}=50\%`$ means full disorder; see Table 1).

The neutron powder diffraction (NPD) study has been done at Institut Laue Langevin (Grenoble, France). High-resolution NPD patterns have been collected at the D2B diffractometer (in its high flux mode with $`\lambda =1.594\mathrm{\AA }`$) at $`T=10\mathrm{K}`$ using the standard orange cryostat. Samples were kept at this temperature for 15 minutes before data collection. Medium-resolution NPD patterns have been collected at D20 ($`\lambda =2.42\mathrm{\AA }`$) diffractometer in the range $`150\mathrm{K}T510\mathrm{K}`$. High-resolution NPD and XRPD data have been analyzed by the Rietveld method using FullProf program.Rodríguez-Carvajal (1993)

In agreement with previous studies, we have found that $`\mathrm{Sr}_2\mathrm{FeMoO}_6`$ NPD pattern can be very well refined with the tetragonal $`I\mathrm{\hspace{0.17em}4}/m`$ space group (SG).D.Sánchez et al. (2002) NPD data reveals that the substitution with La or Ca induces a structural transition. In La substituted samples an orthorhombic splitting of some peaks and the loose of the $`I`$-centering displayed by $`\mathrm{Sr}_2\mathrm{FeMoO}_6`$ become evident.Navarro et al. (2001) A change from $`I\mathrm{\hspace{0.17em}4}/m`$ SG (for $`\mathrm{Sr}_2\mathrm{FeMoO}_6`$) to $`P\mathrm{\hspace{0.17em}2}_1/n`$ SG for $`\mathrm{x}_{\mathrm{La}}0.3`$ and $`\mathrm{x}_{\mathrm{Ca}}0.2`$ takes place. In Glazer’s notation, this corresponds to a change from $`a^0a^0c^{}`$ ($`I\mathrm{\hspace{0.17em}4}/m`$) to $`a^+b^{}b^{}`$ ($`P\mathrm{\hspace{0.17em}2}_1/n`$) tilt system.Woodward (1997) This can be attributed to the small size of La3+ and Ca2+ ions (when compared to that of Sr2+ ions), which reduces the tolerance factor of the perovskite structure, thus inducing the rotation of $`\mathrm{FeO}_6`$ and $`\mathrm{MoO}_6`$ octahedra. Most relevant structural details obtained by NPD at $`10\mathrm{K}`$ are reported in Table 1. The concentration of AS, determined from XRPD, is also given. In all the cases we have checked that the composition is, within the experimental error, the nominal one. In particular, no appreciable deviations from the nominal oxygen content have been found. We have also analyzed the magnetic contribution to the patterns. The large range in $`Q`$ ($`0.4\mathrm{\AA }^1Q7.8\mathrm{\AA }^1`$) of D2B data allows to resolve magnetic and structural parameters without correlations between them. In agreement with previous studies, data in Table 1 indicates that La and Ca doping promotesNavarro et al. (2001) and removesGoodenough and Dass (2000) respectively the degree of Fe/Mo order.

Data in Table 1 reveal a systematic enlargement of the average Mo-O bond-distance ($`d_{\mathrm{Mo}\mathrm{O}}`$) and a shrink of the average Fe-O bond-distance ($`d_{\mathrm{Fe}\mathrm{O}}`$) in the Ca substituted series. Interestingly enough, the different sign of these evolutions almost compensates and the mean (Fe,Mo)-O bond distance ($`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$) remains nearly constant with $`\mathrm{x}_{\mathrm{Ca}}`$. In the La substituted series there is also an enlargement of $`d_{\mathrm{Mo}\mathrm{O}}`$ but $`d_{\mathrm{Fe}\mathrm{O}}`$ remains nearly constant. This leads to an enhancement of the average octahedral size $`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$ that contrasts with the Ca case as illustrated in Fig. 1(a). On the other hand, in both cases there is a clear bending of the mean Fe-O-Mo bond angle ($`\theta _{\mathrm{Fe}\mathrm{O}\mathrm{Mo}}`$) with substitution \[see Fig. 1(b)\]. This is due to the rotation of MO6 octahedra caused by the smaller size of the La3+ and Ca2+ ions when compared to Sr2+. The smaller size of Ca2+, when compared to that of La3+, explains the stronger bond-bending in Ca series (for the same substitution level).

Figure 2 shows the integrated intensity of the $`(\mathrm{1\hspace{0.17em}0\hspace{0.17em}1})`$-$`(\mathrm{0\hspace{0.17em}1\hspace{0.17em}1})`$ doublet (measured at D20) as a function of temperature for both La and Ca substituted compounds. These reflections are basically of magnetic origin (although a small structural contribution exists in both $`I\mathrm{\hspace{0.17em}4}/m`$ and $`P\mathrm{\hspace{0.17em}2}_1/n`$ SG) and thus they can be used to trace the variation of the Curie temperature upon substitution. $`T_C`$ is clearly indicated by a kink in the temperature dependence of the integrated intensity. The remaining intensity above $`T_C`$ in the La case can be mainly attributed to the presence of AS and the resulting AFM order above $`T_C`$.D.Sánchez et al. (2002) Figure 1(c) collects the values of the Curie temperatures estimated from data in Fig. 2. As already noticed in Ref. D.Sánchez et al., 2002, the AFM coupling between nearest-neighbor Fe-Fe pairs occurring in the presence of AS, produces an additional magnetic contribution to the $`(\mathrm{1\hspace{0.17em}0\hspace{0.17em}1})`$-$`(\mathrm{0\hspace{0.17em}1\hspace{0.17em}1})`$ doublet above $`T_C`$ that masks the FM onset in NPD data; indeed the $`\mathrm{x}_{\mathrm{La}}=0.5`$ sample has $`\mathrm{AS}40\%`$ and the determination of $`T_C`$ by NPD data is not accurate. An enhancement of $`T_C`$ of about $`8\mathrm{K}`$ with respect to $`\mathrm{x}_{\mathrm{La}}=0.4`$ compound was reported from magnetization measurements.Navarro et al. (2001) Consequently, for $`\mathrm{x}_{\mathrm{La}}=0.5`$ we have estimated $`T_C477(6)\mathrm{K}`$ \[open square in Fig. 1(c)\]. We note in Fig. 1(c) that Ca substitution promotes a very moderated variation of $`T_C`$: It rises slightly from $`\mathrm{x}=0`$ to $`\mathrm{x}_{\mathrm{Ca}}=0.2`$ and lowers gradually for $`\mathrm{x}_{\mathrm{Ca}}>0.2`$. In contrast, there is an evident growth of $`T_C`$ from $`\mathrm{Sr}_2\mathrm{FeMoO}_6`$ to $`\mathrm{La}_{\mathrm{x}_{\mathrm{La}}}\mathrm{Sr}_{2\mathrm{x}_{\mathrm{La}}}\mathrm{FeMoO}_6`$ ($`\mathrm{x}_{\mathrm{La}}=0.3`$, 0.4 and 0.5).

We turn now to the comparison of the variation of structural parameters and $`T_C`$ for both series. In the case of the isoelectronically substituted Ca-series, it is clear from Fig. 1(a) and (b) that with a monotonic bending of the $`\theta _{\mathrm{Fe}\mathrm{O}\mathrm{Mo}}`$ bond-angle while keeping the $`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$ bond-distance constant, a decrease of $`T_C`$ is found. Therefore closing the $`\theta _{\mathrm{Fe}\mathrm{O}\mathrm{Mo}}`$ bond-angle in $`\mathrm{A}_2\mathrm{FeMoO}_6`$ leads to a weakening of the FM coupling and thus to a reduction of $`T_C`$. The initial increase in $`T_C`$ ($`\mathrm{x}_{\mathrm{Ca}}0.2`$) can be attributed to the reduction of AS observed in the Ca-substituted samples (see Table 1). In contrast, the La series shows a radically different behavior. With similar values of the bond-bending, $`T_C`$ raises as much as $`80\mathrm{K}`$. Hence, it follows that the main difference between the structural evolution of both series that can account for the rising of $`T_C`$ is the expansion of the $`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$ bond in the La-case. The enhancement of the $`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$ bond distance indicates that the substitution of divalent Sr2+ by trivalent La3+ leads to the augmentation of the number of electrons within the metallic sublattice of the double perovskite. Taking into consideration that the available electronic states in both Fe and Mo ions are the $`t_{2g}`$ states that participate in the conduction band,Kobayashi et al. (1998) we can asses that the filling of this band is effectively enhanced with La doping.

Aforementioned spectroscopic measurements on $`\mathrm{La}_\mathrm{x}\mathrm{Sr}_{2\mathrm{x}}\mathrm{FeMoO}_6`$ provide evidences that Mo-band states at the Fermi level become gradually filled upon electron-doping.Navarro et al. (2003) Apparently, data in Table 1, is consistent with this finding: $`d_{\mathrm{Fe}\mathrm{O}}`$ is nearly constant whereas there is a moderated enhancement of $`d_{\mathrm{Mo}\mathrm{O}}`$ ($`\mathrm{\Delta }d_{\mathrm{Mo}\mathrm{O}}0.02\mathrm{\AA }`$) upon La-doping. In agreement with ShannonShannon (1976) this small variation of $`d_{\mathrm{Mo}\mathrm{O}}`$ bond-length would indicate a predominant electron injection at Mo sites.

It is worth to compare the present behavior with that of well known FM manganites where $`T_C`$ is governed by the bandwidth and by the strong electron-phonon coupling (due to the Jahn-Teller effect).Fontcuberta et al. (1996); Zhao et al. (1996); Laukhin et al. (1997) Both parameters, in manganites, strongly depend on the size of the A-cations and the bending of the Mn-O-Mn bond angle drives a strong reduction of $`T_C`$.Fontcuberta et al. (1996) As we have shown here, the dependence of $`T_C`$ on Fe-O-Mo bond angle in double perovskites is much smaller than in manganites. This fact reflects that the strong electron-phonon coupling present in manganites, is not dominant in the present case.

In conclusion, the main structural difference between the two studied series rely on the evolution of the $`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$ bond distance that is constant in Ca case but it is enhanced in the La case. The $`\theta _{\mathrm{Fe}\mathrm{O}\mathrm{Mo}}`$bond angle varying similarly in both series. This indicates that the structural distortion caused by La doping does not significantly alter the FM coupling in $`\mathrm{A}_2\mathrm{FeMoO}_6`$. The enhancement of the $`d_{(\mathrm{Fe},\mathrm{Mo})\mathrm{O}}`$ bond distance in La series signals an effective electron doping in the Fe-Mo sublattice and thus the filling up of the conducting band. Our data conclusively show that the observed reinforcement of the FM coupling in the $`\mathrm{La}_\mathrm{x}\mathrm{Sr}_{2\mathrm{x}}\mathrm{FeMoO}_6`$ series originates from electron-doping effects rather than from structural ones. These findings opens the possibility to design new strategies for further enhancement of $`T_C`$ and shall be of relevance for microscopic understanding of ferromagnetism in double perovskites.

###### Acknowledgements.

We thank the AMORE (EU), MAT 1999-0984-CO3 and MAT 2002-03431 (CICyT, spanish government), and 2001SGR-00334 (Generalitat de Catalunya) projects for financial support. C.F. acknowledges financial support from MCyT (Spain). We thank ILL for the provision beam time.


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# Shot noise of a quantum dot with non-Fermi liquid correlations

## Abstract

The shot noise of a one-dimensional wire interrupted by two barriers shows interesting features related to the interplay between Coulomb blockade effects, Luttinger correlations and discrete excitations. At small bias the Fano factor reaches the lowest attainable value, $`1/2`$, irrespective of the ratio of the two junction resistances. At larger voltages this asymmetry is power-law renormalized by the interaction strength. We discuss how the measurement of current and these features of the noise allow to extract the Luttinger liquid parameter.

A comprehensive understanding of the transport properties of mesoscopic conductors can be achieved with the study of both the average current and its fluctuations. Unlike equilibrium noise, linked to the conductance by the fluctuation-dissipation theorem, shot noise provides further understanding not related to the average current. Noise is typically very sensitive to correlation mechanisms arising either due to statistics, interference phenomena and interactions deJong97 ; blanter00 . One of the most striking effects recently observed is the measurement depicciotto97 ; saminadayar97  of the fractional charge in the Fractional Quantum Hall Effect.

The understanding of the role of electron interaction on shot noise is far from being complete. At the present most of the attention is devoted to two classes of systems, mesoscopic junctions in the Coulomb blockade regime and one dimensional (1D) wires where electron interaction lead to a Luttinger liquid behaviour. In single electron tunnelling transistors noise has been studied both in the sequential tunnelling davies92 ; hershfield93 ; hanke93 ; korotkov94  and in the cotunnelling averin00 ; sukhorukov00  regime. Deviation of the shot noise from the Poisson value was predicted when two charge states are almost degenerate. As a function of the transport voltage, the Fano factor shows dips in correspondence of the steps of the Coulomb staircase. Experiments on the shot noise suppression due to Coulomb blockade effects has been performed by Birk et al. birk95  with a good agreement with the theoretical prediction. As a function of the gate voltage, shot noise exhibits a periodic suppression below the Poisson value hanke93 .

Another situation where interactions have a drastic consequence v95  is in 1D systems. Here, there are no fermionic quasiparticle, and the low energy excitations consist of independent long-wavelength oscillations of the charge and spin density, which propagate with different velocities. The density of states has a power-law behaviour and the transport properties cannot be described in terms of the conventional Fermi-liquid approach. A Luttinger liquid (LL) with an arbitrarily small barrier leads to a complete suppression of transport at low energies kane92 . By now there are several works which show the emergence of a LL behaviour. These studies embrace a variety of physical systems as quantum wires auslaender00 , carbon nanotubes bockrath99  and edge state in the Fractional Quantum Hall effect milliken96 . Shot noise in systems with LL correlations provides important informations and a number of very interesting properties have been found so far. In addition to the possibility to measure the fractional charge, interactions renormalize the singularity at the “Josephson” frequency chamon96 . Other clear signatures include the complete locking of the shot noise in coupled LL trauzettel02 . We thus expect that a single electron transistor made of a 1D system will have a rather rich phenomenology.

In this Letter we study the shot noise of a quantum dot, formed by two barriers, in a 1D wire with LL correlations in the sequential tunnelling regime. We consider the quantum dot with discrete energy excitations, ranging from the “single resonant level” to a continuum distributions. Beside the suppression of the shot noise due to the Coulomb blockade hershfield93 , we find additional effects induced by the non-Fermi liquid correlations. These last features are what we are mainly looking at. We show that the shot noise reveals several unambiguous evidences of Luttinger correlations and presents new and complementary informations with respect to the current measurements. The results can be used to test independently the non-Fermi liquid nature of the system.

The Hamiltonian of the system is composed by the term which describes electrons in the quantum wire and the scattering induced by the presence of the two barriers. In the bosonized form the part due to an homogeneous spinless interacting one-dimensional electron gas is expressed in terms of an harmonic field operators ($`\mathrm{}=1`$) $`[\mathrm{\Pi }(x),\mathrm{\Theta }(x^{})]=i\delta (xx^{})`$v95

$$H_0=\frac{v_\mathrm{F}}{2}dx\left\{\mathrm{\Pi }^2(x)+\frac{1}{g^2}[_x\mathrm{\Theta }(x)]^2\right\}.$$
(1)
The interaction parameter is $`g^2=1+V(q=0)/\pi v_\mathrm{F}`$ with $`v_\mathrm{F}`$ the Fermi velocity and $`V(q)`$ the Fourier transform of the electron-electron interaction. The excitations of Eq.(1), at fixed average density $`\rho _0=k_\mathrm{F}/\pi `$, are collective density waves with dispersion $`\omega (q)=v_\mathrm{F}|q|/g`$. The scattering is due to the left (l) and to the right (r) barriers at positions $`x=\pm d/2`$ with different heights $`U_{\mathrm{l},\mathrm{r}}`$. The corresponding tunnelling Hamiltonian is kane92

$$H_\mathrm{T}=\underset{p=\pm }{}(U_\mathrm{l}+pU_\mathrm{r})\underset{s=\pm }{}\mathrm{cos}\pi (N^s+n_0\delta _{s,}\frac{1p}{4})$$
(2)
where $`N^\pm =[\mathrm{\Theta }(d/2)\pm \mathrm{\Theta }(d/2)]/\sqrt{\pi }`$, with $`N^{}`$ the deviation of the number of electrons in the dot from the mean value, $`n_0=d\rho _0`$, and $`N^+/2`$ the imbalanced electrons between the left and right leads. The coupling to the source-drain bias $`V`$ and the gate voltage $`V_\mathrm{g}`$ is given by $`H_\mathrm{V}=e(VN^+/2+\alpha V_\mathrm{g}N^{})`$, with $`\alpha `$ the ratio between gate and total capacitances.

The zero-frequency power spectrum of the noise is given by the current-current correlation function

$$S=\underset{\mathrm{}}{\overset{\mathrm{}}{}}𝑑t\left[\delta I(t)\delta I(0)+\delta I(0)\delta I(t)\right],$$
(3)
where $`\delta I(t)I(t)I`$ is the (total) current fluctuation operator with respect to the average $`I`$. Since we are interested in the zero-frequency noise, due to continuity equation and simmetries of the correlation functions, it is sufficient to study fluctuations in the current through the right or the left junctions $`I_{\mathrm{r}/\mathrm{l}}(t)=e\dot{\mathrm{\Theta }}(\pm \frac{d}{2},t)/\sqrt{\pi }`$.

The current fluctuations are determine by the dynamics of the variables $`N^\pm `$ under the influence of the electrostatic fields in the tunnelling potential (2). We consider the sequential tunnelling regime, neglecting contributions from coherent processes. This assumption is valid in the weak tunneling regime for not too low temperatures braggio01 . This is exactly the regime relevant for available experiments. For high barriers the dynamics is dominated by tunnelling through the left and right junctions with resistances $`R_\mathrm{l}`$ and $`R_\mathrm{r}`$ respectively. There are two characteristic energy scales. The energy $`E_\mathrm{c}`$ has to be supplied in order to transfer one extra charge to the island from the neutral configuration. It determines the dot ground state chemical potential with $`n`$ electrons $`\mu (n)=2E_\mathrm{c}(nn_\mathrm{g})`$, with $`n_\mathrm{g}=n_0+\alpha eV_\mathrm{g}/2E_\mathrm{c}1/2`$. A discrete energy $`\epsilon `$ is necessary to further excite the discrete plasmon modes inside the dot. An explicit expression of these two energy scales depends on the microscopic and circuital details of the system braggio01 . The coupling to gates and the presence of possible long range electron interactions tend to modify these values k00 . For these reasons we will treat them as independent parameters.

The shot noise is obtained from the solution of a time dependent master equation for the occupation probabilities of charges in the dot as described in Ref. hershfield93, . The new ingredients here are the tunnelling rates that depend on the Luttinger correlations braggio01 . For a tunnelling process, to which is associated a change $`E`$ in the electrostatic energy, the rate is proportional to $`\gamma (E)=_{p=0}^{\mathrm{}}\mathrm{\Gamma }(p+1/g)f(Ep\epsilon ,g)/p!`$, with $`f(E,g)=\mathrm{e}^{E/2T}|\mathrm{\Gamma }\left(1/(2g)+iE/2\pi T\right)|^2`$ ($`k_\mathrm{B}=1`$). Note that this expression is obtained by assuming a thermal distribution for the plasmons in the leads and in the dot with $`T\epsilon `$. This implies that the initial dot state is always the ground state. The plasmon excitations are present only in the final states. Such a description is appropriated when the relaxation processes are faster than the tunnelling processes. In this case any excited state will decay into the ground state long before the next electron tunnels in the dot. The possibility to tune the external bias voltage in the energy $`E`$ allow to investigate the discreteness of the plasmon energy, ranging from the “single resonant level” ($`E<\epsilon `$) where no plasmon are excited, to the continuum of plasmon distribution ($`E\epsilon `$). In these two extreme cases the rates acquire the simplifed form $`\gamma (E)f(E,g)`$ and $`\gamma (E)f(E,g/2)`$ respectively. In the first case the power law correlations are only due to the Luttinger liquid nature of the leads. In the latter the dot itself acts as a Luttinger reservoir.

In the following we will present the case of asymmetric barriers characterized by ratio $`R=R_\mathrm{r}/R_\mathrm{l}`$. As we are interested in the shot noise we consider only low temperatures $`TeV`$. We will consider results for the Fano factor $`FS/2e|I|`$. A detailed discussion of the behavior of the average current as a function of the external voltages as been given in braggio01 . The Fano factor is presented in Fig. 1 with $`R=10`$ and $`T=0`$ for two different ratio $`\epsilon /E_\mathrm{c}=0.1`$ (a) and $`\epsilon /E_\mathrm{c}=1.6`$ (b). These two values are chosen in order to show the different effects of the discrete plasmon modes. The noise is periodic in the $`n_\mathrm{g}`$-variable. For clarity in the figure we present the results for $`1/2<n_\mathrm{g}<3/2`$ where two Coulomb peaks of the linear conductance, centered at $`n_\mathrm{g}=0,1`$, are present . Different features of electron-electron interactions will be now described depending on the small, large and intermediate voltage regions. The numerical results can be corroborated by analytical calculations in several limits.

Let us start with the small voltage limit. Near to the resonance $`n_\mathrm{g}0`$, for $`eV<4E_\mathrm{c}`$ two charge values contribute predominantly to the transport. The Coulomb blockade region are here delimitated by the diamond lines $`E_\pm eV/2\pm 2E_\mathrm{c}n_\mathrm{g}=0`$. In this regime the Fano factor assumes the form

$$F=1\frac{2R\gamma _+\gamma _{}}{[(1+e^{E_{}/T})\gamma _{}+R(1+e^{E_+/T})\gamma _+]^2}$$
(4)
with $`\gamma _\pm \gamma (E_\pm )`$. By inspection of (4) one can see that the temperature plays a significant role only near the edges of the diamond lines $`|E_+|T`$ or $`|E_{}|T`$ (see later). Out from this region the Fano factor is well approximated by the $`T=0`$ value. We first discuss the case of low bias voltages $`E_\pm <\epsilon `$ where it is not possible to excite plasmons. At $`T=0`$ the Fano is $`F=(E_{}^{\mathrm{\hspace{0.17em}2}\nu (g)}+R^2E_+^{\mathrm{\hspace{0.17em}2}\nu (g)})/(E_{}^{\nu (g)}+RE_+^{\nu (g)})^2`$, with $`\nu (g)=1+1/g`$. For non-interacting leads ($`g=1`$) $`F`$ is voltage independent $`F=(1+R^2)/(1+R)^2`$ and assumes the lowest value ($`F=1/2`$) only for symmetric barriers.

In the interacting case $`g<1`$ the Fano is always suppressed to the $`1/2`$ value, at a given voltage ratio $`4E_\mathrm{c}n_\mathrm{g}/eV=(1R^{1/\nu (g)})/(R^{1/\nu (g)}+1)`$ . On increasing the interaction strength ($`g0`$) the resonant point moves towards $`n_\mathrm{g}=0`$; away from it $`F`$ tends to the Poisson value (see Fig. 1(b) at $`eV<4E_\mathrm{c}`$, and Fig. 2). This behaviour is also confirmed by the temperature scaling near to the edges of the Coulomb blockade region. In the limits $`|E_\pm |T`$ one has

$$F1c_\pm (T/eV)^{\nu (g)},$$

with $`c_\pm R^{\pm 1}`$. For non-interacting leads, $`F`$ is temperature independent, increasing the interactions the Fano factor approaches as a power law the values $`F=1`$. If $`\epsilon E_\mathrm{c}`$ (Fig. 1(a)) one can also reach the regime $`\epsilon E_\pm `$, still using only two charge states, $`eV<2E_\mathrm{c}`$. In this case the Fano factor results from the contribution by the continuum of excited plasmons. Its expression as a function of resistance and voltages is still valid but with the replacement $`\nu (g)\nu (g/2)`$.

The strong interplay between Coulomb blockade features and non-Fermi liquid correlations is also very clearly revealed at larger voltages $`eV4E_\mathrm{c}`$, if the asymmetry of the barriers is not too small. As a function of the voltage bias and in the limit $`eV\epsilon `$, (cf. Fig. 3) the Fano factor shows a series of dips and it saturates to a constant value, $`F_{\mathrm{}}`$, for $`eVE_\mathrm{c}`$. In the orthodox theory of Coulomb blockade in small metal junctions, the decrease of the Fano factor is driven by $`E_\mathrm{c}`$ and it is attributed to the correlations present at the degeneracy points. A detailed analysis of the numerical results allows to extract the following behaviour, valid for enough strong asymmetry $`R1`$, for the distance in the bias voltage between two successive dips at fixed voltage gate $`\delta V_{\mathrm{dip}}`$

$$\frac{e\delta V_{\mathrm{dip}}}{4E_\mathrm{c}}=\frac{R^{1/\nu (g/2)}+1}{R^{1/\nu (g/2)}1},$$
(5)
This fitting behaviour is obtained by extrapolating, at larger voltages, the dip position lines $`eV(n)(1R^{1/\nu (g/2)})=4E_\mathrm{c}(n_\mathrm{g}n)(R^{1/\nu (g/2)}+1)`$ founded previously, in the continuum case for the $`n`$ and $`n+1`$ charges, and considering the corresponding distance $`\delta V_{\mathrm{dip}}V(n+1)V(n)`$.

In the asymptotic regime we find substancial modifications also to the Fano-Schottky theorem $`F_{\mathrm{}}=(1+R^2)/(1+R)^2`$ hershfield93 . We extract the power law behaviour

$$F_{\mathrm{}}=\frac{1+R^{2/\nu (g/2)}}{[1+R^{1/\nu (g/2)}]^2}.$$
(6)
We can see that Luttinger correlations lead, instead of $`R`$, a new effective resistance ratio $`R^{1/\nu (g/2)}`$ that scales with a power law in $`g`$, in agreement with the results at small voltages. The properties of the Fano factor given so far, allow to extract the properties of the transistor and the value of the Luttinger liquid parameter without resorting to any fitting procedure.

Let us switch now to the more intricate region $`eV2E_\mathrm{c},\epsilon `$, where Coulomb features, discrete nature of the excited plasmon states, and Luttinger correlations are present simultaneously (cf. Fig. 1(b)). Apart from the asymptotic regime $`eVE_\mathrm{c},\epsilon `$, where $`FF_{\mathrm{}}`$ as in (6), the physics is quite different depending on the intensity of the interaction. For strong interactions, $`g<1/2`$, $`F`$ is similar to the one described above in the continuum limit. Qualitative differences are instead revealed in the weak interaction limit $`1/2<g<1`$. Here, the threshold of the Coulomb dips is not renormalized by the interaction. Moreover superimposed to these dips there is an additional structure with a width proportional to $`|\epsilon 2E_\mathrm{c}|`$. These new features are due to the transport via excited states. Note that the effect of correlations in these channels can also lead to a change of the curvature in the Fano factor, differently from the processes associated with the ground state to ground state transitions. This is visible by looking at the different colors of the diamont-like structures (e.g. red and green features in Fig. 1(b) for $`g=1`$). These two colors represent the two different way of entering/leaving in/from a plasmon excited state of the dot. Indeed, by considering the $`nn+1n`$ transition, we can have either one electron that enters in the dot, creating an excited plasmon state of the $`n+1`$ charge or one elctron that leaves the dot from the $`n+1`$ ground state in an excited plasmon state of $`n`$ charges. These two processes can be discriminated in the Fano behaviour giving informations on the different excited states that contribute to transport.

In conclusion we demonstrated how the presence of Luttinger correlations changes drastically the behaviour of the Fano factor with respect to the orthodox theory. In particular we showed that the interaction strongly renormalizes the position of the dips, filtering at small voltages the degrees of correlations. A crucial role is played by the barrier asymmetry that is shown to be power law renormalized by the interaction strength. Very recently Nazarov and Glazman nazarov02  obtained the renormalization group equation for the transmission in one-dimensional wire interrupted by a double-barrier structure with a resonant level. It would be important to extend the results on noise beyond the sequential tunnelling approximation by emplying the approach of Ref. nazarov02 . We expect that the predictions made in this work are amenable of experimental verification. Indeed realizations of the one-dimensional quantum dot system we considered has been recently achieved in a cleaved-edge overgrowth quantum wire with two impurities auslaender00  and in carbon nanotubes with buckles postma01 . Experimental results are already available on the linear and non-linear transport current. New experiments on the shot noise would be of interest in order to test the new predictions presented in this work.

Acknowledgements: This work has been supported by Italian MURST via PRIN 2000, by the EU within the programmes RTN2-2001-00440, HPRN-CT-2002-00144.


text:
# Quantum dynamics of exchange biased Single Molecule Magnets

## Abstract

We present a new family of exchange biased Single Molecule Magnets in which antiferromagnetic coupling between the two components results in quantum behaviour different from that of the individual SMMs. Our experimental observations and theoretical analysis suggest a means of tuning the quantum tunnelling of magnetization in SMMs.

Various present and future specialized applications of magnets require monodisperse, small magnetic particles, and the discovery of molecules that can function as nanoscale magnets was an important development in this regard . These molecules act as single-domain magnetic particles that, below their blocking temperature, exhibit magnetization hysteresis, a classical property of macroscopic magnets. Such single-molecule magnets (SMMs)  straddle the interface between classical and quantum mechanical behaviour because they also display quantum tunnelling of magnetization  and quantum phase interference . Quantum tunnelling of magnetization can be advantageous for some potential applications of SMMs, for example, in providing the quantum superposition of states required for quantum computing. However, it is a disadvantage in other applications, such as information storage, where it would lead to information loss. Thus it is important to both understand and control the quantum properties of SMMs. Here we present a new family of supramolecular SMM dimers  in which antiferromagnetic coupling between the two components results in quantum behaviour different from that of the individual SMMs. Our experimental observations and theoretical analysis suggest a means of tuning the quantum tunnelling of magnetization in SMMs.

The compound has the formula

\[Mn4O3Cl4(O2CEt)3(py)3\] (hereafter Mn4). The preparation, X-ray structure, and detailed physical characterization have been reported . The complex has a distorted cubane-like core geometry and is Mn$`{}_{}{}^{\mathrm{III}}{}_{3}{}^{}`$MnIV. Strong superexchange coupling between the spins leads to a well isolated $`S=9/2`$ ground state. Mn4 crystallizes in the hexagonal space group R3(bar) with pairs of Mn4 molecules lying head-to-head on a crystallographic S6 symmetry axis (Fig. 1). Thus, each M4 has C3 symmetry and the \[Mn4\]2 dimer has S6 symmetry. This supramolecular arrangement is held together by six C-H$`\mathrm{}`$Cl hydrogen bonds (dashed lines in Fig. 1) between the pyridine (py) rings on one Mn4 and Cl ions on the other. The C-H$`\mathrm{}`$Cl hydrogen bonds in \[Mn4\]2 have C$`\mathrm{}`$Cl distances and C-H$`\mathrm{}`$Cl angles of 0.371 nm and 161.57, respectively, typical of this type of hydrogen bond. The \[Mn4\]2 dimer also brings the central bridging Cl ions of each Mn4 close together (0.3858 nm, dotted line in Fig. 1), almost at their Van der Waals separation (0.36 nm). Each \[Mn4\]2 is rather well separated from neighboring dimers. The supramolecular linkage within \[Mn4\]2 introduces exchange interactions between the M4 molecules via both the six C-H$`\mathrm{}`$Cl pathways and the Cl$`\mathrm{}`$Cl approach. All these seven interactions are expected to be weak, but combined they will lead to noticeable antiferromagnetic coupling between the Mn4 units.

Antiferromagnetic coupling between the M4 units in \[Mn4\]2 results in the latter being an excellent candidate for the study of quantum tunnelling in a system of truly identical, antiferromagnetically-coupled particles with a ground state S = 0. Such a system has long been sought for study after the theoretical conclusion  that tunnelling in antiferromagnets is much more pronounced than in ferromagnets.

Tunnelling studies on \[Mn4\]2 were performed by magnetization measurements on single crystals using an array of micro-SQUIDs . Fig. 2 shows typical hysteresis loops in magnetization versus magnetic field scans with the field applied nearly along the easy axis of magnetization of \[Mn4\]2, that is, parallel to the S6 axis . These loops display step-like features separated by plateaus. The step heights are temperature-dependent above 0.3 K; below this, the loops become temperature-independent. As discussed below, the steps are due to resonant quantum tunnelling of the magnetization (QTM) between the energy states of the \[Mn4\]2 dimer.

QTM has been previously observed for several SMMs , but the novelty for \[Mn4\]2 is that the QTM is now the collective behavior of the complete $`S=0`$ dimer of exchange-coupled $`S=9/2`$ Mn4 quantum systems. This coupling is manifested as an exchange bias of all tunnelling transitions, and the resulting hysteresis loop consequently displays unique features, such as the absence for the first time in a SMM of a QTM step at zero field.

Before interpreting the hysteresis loops further, we discuss a simplified spin Hamiltonian describing the \[Mn4\]2 dimer. Each M4 SMM can be modeled as a giant spin of $`S=9/2`$ with Ising-like anisotropy. The corresponding Hamiltonian is given by

$$_i=DS_{z,i}^2+_{\mathrm{trans},i}+g\mu _\mathrm{B}\mu _0\stackrel{}{S_i}\stackrel{}{H}$$
(1)
where $`i=1`$ or 2 (referring to the two M4 SMMs of the dimer), $`D`$ is the uniaxial anisotropy constant, and the other symbols have their usual meaning. Tunnelling is allowed in these half-integer ($`S=9/2`$) spin systems because of a small transverse anisotropy $`_{\mathrm{trans},i}`$ contains $`S_{x,i}`$ and $`S_{y,i}`$ spin operators and transverse fields ($`H_x`$ and $`H_y`$). The exact form of $`_{\mathrm{trans},i}`$ is not important in this discussion. The last term in Eq. 1 is the Zeeman energy associated with an applied field. The Mn4 units within the \[Mn4\]2 dimer are coupled by a weak superexchange interaction $`J`$ via both the six C-H$`\mathrm{}`$Cl pathways and the Cl$`\mathrm{}`$Cl approach. Thus, the Hamiltonian ($``$) for \[Mn4\]2 is

$$=_1+_2+J\stackrel{}{S_1}\stackrel{}{S_2}$$
(2)
where $`S_1=S_2=9/2`$. The $`(2S_1+1)(2S_2+1)=100`$ energy states of the dimer can be calculated by exact diagonalization and are plotted in Fig. 3a as a function of applied field along the easy axis. Each state of \[Mn4\]2 can be labelled by two quantum numbers $`(M_1,M_2)`$ for the two Mn4 SMMs, with $`M_1=9/2,7/2,\mathrm{},9/2`$ and $`M_2=9/2,7/2,\mathrm{},9/2`$. For the sake of simplicity, we do not discuss the mixing with other spin states that is due to transverse anisotropy terms, that is $`_{\mathrm{trans},i}=0`$.

At very low temperature, most of the excited spin states are not populated and can be neglected. Thus, Fig. 3b shows only the low-lying states involved in the magnetization reversal at very low temperature when sweeping the field from a high negative field to a positive one. At high negative field, the initial state is $`(M_1,M_2)=(9/2,9/2)`$, that is, both molecules are in the negative ground state. As the field is swept, the first (avoided) level crossing is at -0.33 Tesla. There is a non-zero probability, which depends upon the sweep rate, for the magnetization to tunnel from $`(9/2,9/2)`$ to $`(9/2,9/2)`$. (For convenience, we do not list here (or below) both degenerate $`(M,M^{})`$ and $`(M^{},M)`$ states). The smaller the sweep rate the larger is the tunnelling probability, i.e. the larger is the resulting step in Fig. 2b. At field values away from the avoided level crossing, the dimer states are frozen by the significant magnetic anisotropy barrier.

At the next level crossing at 0 T, there is the possibility of tunnelling from $`(9/2,9/2)`$ to $`(9/2,9/2)`$, but this requires both Mn4 molecules of the dimer to tunnel simultaneously. The corresponding tunnelling probability is very small and can hardly be seen in Fig. 2. At the next level crossing at 0.2 T, the dimer can undergo tunnelling from $`(9/2,9/2)`$ to $`(9/2,7/2)`$, corresponding to one of the Mn4 molecules tunnelling from the ground state to an excited state, followed by rapid relaxation from $`(9/2,7/2)`$ to $`(9/2,9/2)`$ (curly arrow in Fig. 3b). At the next level crossing at 0.33 T, the situation is analogous to that at -0.33 T, and the dimer can undergo tunnelling from $`(9/2,9/2)`$ to $`(9/2,9/2)`$. Between 0.33 and 0.75 T, there are several level crossings from $`(9/2,9/2)`$ to excited states that require simultaneous tunnelling in both Mn4 units and can be neglected. The level crossing at 0.75 T allows tunnelling from $`(9/2,9/2)`$ to $`(9/2,5/2)`$, followed by relaxation from $`(9/2,5/2)`$ to $`(9/2,7/2)`$ and $`(9/2,9/2)`$. At 0.87 T tunnelling can occur from $`(9/2,9/2)`$ to $`(7/2,9/2)`$, followed by relaxation from $`(7/2,9/2)`$ to $`(9/2,9/2)`$. Finally, at 1.4 T tunnelling can occur from $`(9/2,9/2)`$ to $`(5/2,9/2)`$, followed by relaxation from $`(5/2,9/2)`$ to $`(9/2,9/2)`$. The values of $`D`$ and $`J`$ used in Fig. 3 were calculated from the field positions of the steps in the hysteresis loops, ignoring transverse (and fourth order) anisotropy terms. The calculated values are $`D`$ -0.72 K and $`J`$ +0.1 K. The former is very close to those determined experimentally for several (isolated) Mn4 SMMs , and the latter is antiferromagnetic (positive value) and very weak, as expected for an exchange interaction via the six C-H$`\mathrm{}`$Cl and the Cl$`\mathrm{}`$Cl pathways. A value of $`J0.1`$ K was also obtained from susceptibility determinations using hysteresis loops measured in the 1 to 8 K range (Fig. 4).

We tried to get a deeper insight into the relaxation processes by relaxation measurements at constant applied field for initially saturated or demagnetized magnetization (Fig. 5). The relaxation paths of the former are analogous to those of hysteresis loops (Fig. 2) whereas the latter starts in an initial state of $`(9/2,9/2)`$ for nearly all dimers. Thus, transitions (2) and (4) should not occur that can be seen well in Fig. 5. Furthermore, this shows that only few dimers relaxe via transitions (4) of initially saturated magnetization. Note that all transitions are not well resolved, due to significant broadening by dipolar effects and small exchange coupling between neighboring dimers.

Relaxation data were determined from DC relaxation decay measurements: first a field of 1.4 T was applied to the sample at 5 K to saturate the magnetization in one direction, and the temperature lowered to a chosen value between 1 and 0.04 K. The field was then swept to 0 T at 0.28 T/s and the magnetization in zero field measured as a function of time (Fig. 6). From these data, relaxation times could be extracted which allows the construction of an Arrhenius plot (Fig. 7) which contains several distinct features. Above ca. 0.3 K the relaxation rate is temperature-dependent with $`\tau _0=3.8\times 10^6`$ s and $`U_{\mathrm{eff}}=`$ 10.7 K. Below ca. 0.3 K however, the relaxation rate is temperature-independent with a relaxation rate of $`8\times 10^5`$ s indicative of QTM between the ground states.

The above results demonstrate that even weak exchange interactions can have a large influence on the quantum properties of SMMs. From one viewpoint, each half of the \[Mn4\]2 dimer acts as a field bias on its neighbor, shifting the tunnel resonances to new positions relative to isolated Mn4 molecules. In particular, the latter show a strong QTM step at zero field in the hysteresis loop , a feature absent for \[Mn4\]2 (Fig. 2) because this would be a double quantum transition with a very low probability of occurrence. The absence of tunnelling at zero-field is important if SMMs are to be used for information storage, and the option is still retained to switch on tunnelling, if and when required, by application of a field. Thus, future studies will probe this double transition at zero field in \[Mn4\]2, and the corresponding multiple quantum transition in higher supramolecular aggregates of SMMs, including determining their exact probability of occurrence and to what extent this can be controlled by the degree of aggregation, variation of exchange coupling strength, and similar modifications. From another viewpoint, \[Mn4\]2 represents an unequivocal and unprecedented example of quantum tunnelling in a monodisperse antiferromagnet with no uncompensated spin (i.e. $`S=0`$) in the ground state. Thus, \[Mn4\]2 and related species will prove invaluable for detailed studies of this phenomenon. Finally, the absence of a level crossing at zero field also makes the \[Mn4\]2 dimer a very interesting candidate as a qubit for quantum computing, because the ground state is the entangled combination of the $`(9/2,9/2)`$ and $`(9/2,9/2)`$ states; the coupling of this $`S=0`$ system to environmental degrees of freedom should be small, which means decoherence effects should also be small.

In future work, we shall use the Landau-Zener method to determine the tunnel splitting in \[Mn4\]2, and apply a transverse field to probe its exact influence on QTM rates (we have already confirmed that a transverse field increases the tunnelling rate, as expected for QTM). The identification of both an antiferromagnetic coupling and an exchange-bias effect in \[Mn4\]2 demonstrates the feasibility of employing supramolecular chemistry for modulating the quantum physics of SMMs, providing a realistic general method to fine-tune the properties of these molecular nanoscale materials. This brings closer their use in devices.