text:
# Transition-metal interactions in aluminum-rich intermetallics

## I Introduction

Total-energy calculations are an important tool in theoretical condensed-matter physics, giving insight into structures and mechanical properties of solids . Accurate calculations of total energy are notoriously difficult, however. Theoretically, one must solve the Schrödinger equation simultaneously for all electrons in the presence of fixed atomic nuclei. Density-functional theory (DFT)  simplifies this problem by reducing it to the self-consistent solution of Schrödinger’s equation for a single electron in a potential that depends upon the electron density. Even with this simplification, full ab-initio DFT electronic-structure methods are computationally demanding , usually limited to systems of less than a hundred atoms, and may not yield immediate physical insight once an answer is obtained.

Instead, one may expand the total energy in terms of pair and many-body interatomic potentials , so that the total energy appears as an explicit function of atomic separations. Depending on the physical system under study and the type of information sought, the expansion may often be truncated after a small number of terms. Such a truncated expansion trades off a degree of accuracy in favor of computational simplicity and potentially greater physical insight as compared with a full ab-initio electronic-structure approach.

Many metallic systems been studied using such quantum-based interatomic potentials, including aluminum and its alloys with both transition and non-transition metals . These potentials are especially simple in the case of non-transition metals. There, the $`d`$-electron energy bands are either empty or else are completely filled and deeply buried below the Fermi energy level, allowing rapidly convergent expansions of the total energy and an accurate description in terms of only radial-force interactions . The presence of partially filled $`d`$-bands at or near the Fermi level in transition metals complicates the analysis. The occupied $`d`$-band electronic states are highly localized in the vicinity of the atoms, leading to directional or covalent bonding with a strong angular dependence. Consequently, total-energy expansions will not converge as quickly as for non-transitions metals, and three- and higher-body angular-force interactions may contribute significantly .

Moriarty  has developed a rigorous DFT treatment of interatomic potentials for transition metals (TMs) in the context of the generalized pseudopotential theory (GPT). The treatment was later extended to binary and ternary alloys of aluminum with first row transition metals . These studies found that three- and four-body interactions could be important in determining thermodynamic and mechanical stability of structures with large TM concentrations. The explicit treatment of $`d`$-electron interactions in the GPT produces a strong attractive interaction at unphysically short distances in the pair potentials, which is balanced by repulsive forces contained in the many-body interactions. For specific structural environments, however, it is possible to directly modify the short-ranged part of the TM-TM pair potentials to remove this unphysical attraction, so that a truncation of the total energy expansion at the level of pair potentials will be more accurate when transition metal atoms are near neighbors. Here we wish to consider the construction of such effective pair potentials for important transition-metal aluminide systems.

One motivation for this study is the need for fast total-energy calculations in Al-TM systems with short TM-TM separations to enable structural relaxation, and more generally, molecular-dynamics and Monte-Carlo simulations. We focus our attention on Al-Co-Ni compounds in decagonal quasicrystalline structures . The precise modifications required in the Co-Co, Co-Ni, and Ni-Ni pair potentials depend on the particular structure studied, but they should be at least approximately valid for many similar structures. Furthermore, the modifications obtained may allow us to treat Al-Co-Cu and Al-Cu-Ni decagonal phases  because the Cu-Cu interactions do not appear to require modification . Limited numbers of ab-initio electronic-structure calculations, which effectively sum the pair and many-body total-energy contributions, are sufficient to determine the required modifications, and this is the strategy that we follow here.

We intend to apply these potentials to predict the structures of decagonal quasicrystals . A great deal of experimental data is available that identifies the positions of most atoms and identifies the chemical identity of many of those. However, in order to determine the quasicrystal structures from X-ray diffraction, one faces degenerate structures because elements near each other in a row of the periodic table (such as Co, Ni and Cu) have similar X-ray form factors. A common approach to this problem is to supplement the experimental data with total-energy calculations. This approach is well established in crystallography .

The effective pair potentials developed here can be applied to total energy calculations in quasicrystals and related structures with a great reduction in computational times compared with the ab initio electronic-structure calculations themselves. The time savings results from two general features of the potentials. First, for a given atomic volume and composition the potentials may be precalculated and then applied repeatedly with a simple lookup and interpolation. Second, to calculate the change in energy when a single atom is moved, only interactions affecting that atom are needed. If the interactions are cut off at a finite spatial separation, the time required to calculate the change in total energy becomes independent of the number of atoms in the complete structure. This is so-called order-$`N`$ scaling. In contrast, ab-initio electronic-structure methods must recalculate the entire system when a single atom is moved, typically resulting in order-$`N^3`$ scaling.

In Sec. II, GPT interatomic potentials are briefly reviewed and the issues surrounding the truncation of the total energy expansion at the pair-potential level in Al-TM systems are discussed. Section III gives details about the scheme we employ to determine the needed modifications to the TM-TM pair potentials. In Sec. IV, we discuss the results of our full ab-initio electronic-structure calculations and the modified TM-TM pair potentials developed using them.

## II GPT Interatomic Potentials

The generalized pseudopotential theory starts with a full ab-initio DFT representation of the total energy in the standard local-density approximation (LDA). The usual small-core approximation is used to separate the treatment of valence and core electrons and the electron-ion interaction for the valence electrons is handled by means of optimized nonlocal pseudopotentials. A mixed valence-wavefunction basis is employed allowing $`sp`$ states to be represented as superpositions of plane waves, while $`d`$ states are represented in terms of localized, atomic-like $`d`$ states. The electron density and total energy are systematically expanded in terms of the resulting weak matrix elements in this basis: $`sp`$ pseudopotential matrix elements $`W_{kk^{}}`$, $`sp`$-$`d`$ hybridization matrix elements $`\mathrm{\Delta }_{kd}`$ and $`S_{kd}`$, and $`d`$-$`d`$ tight-binding-like matrix elements $`\mathrm{\Delta }_{dd^{}}`$ and $`S_{dd^{}}`$. In real space, the total energy may be cast in terms of well-defined interatomic potentials, which can be calculated as functionals of these matrix elements. For a general multicomponent alloy, the GPT total-energy expansion takes the form

$$E_{\mathrm{tot}}(\stackrel{}{R}_i)=NE_{\mathrm{vol}}(\mathrm{\Omega },𝐜)+\frac{1}{2}\underset{\alpha \beta }{}\underset{ij}{}^{}v_2^{\alpha \beta }(R_{ij};\mathrm{\Omega },𝐜)+\frac{1}{6}\underset{\alpha \beta \gamma }{}\underset{ijk}{}^{}v_3^{\alpha \beta \gamma }(R_{ij},R_{jk},R_{ki};\mathrm{\Omega },𝐜)+\mathrm{},$$
(1)
where $`\stackrel{}{R}`$ is the set of all positions of $`N`$ ions in the metal, $`E_{\mathrm{vol}}`$ is a volume term that includes all collective and one-ion contributions that are independent of structure, and $`v_2^{\alpha \beta }`$, $`v_3^{\alpha \beta \gamma },\mathrm{}`$ are the two-, three-, and higher many-ion interatomic potentials. The primes on sums over ion positions exclude all self-interaction terms. Indices $`\alpha ,\beta ,\gamma ,\mathrm{}`$ run over all chemical species, and indices $`i,j,k,\mathrm{}`$ run over the individual ion positions. The volume term and all of the interatomic potentials depend on the atomic volume $`\mathrm{\Omega }`$ and a composition vector $`𝐜`$, but are independent of structure. The potentials are functions of the relative positions of small subsets of atoms, independent of the positions of all other atoms in the system. The entire dependence on the structure comes analytically through the summations over ion positions. This makes these potentials transferable among different structures at fixed atomic volume and composition. The full details of the first-principles GPT for transition-metal systems are given in Refs.  and . A simplified model version of the theory has also been developed , using canonical $`d`$-bands to obtain analytic representations of the multi-ion potentials.

In general, the separation of the total energy into two- and higher-body terms is not entirely unique, since one can always add contributions to the pair potential $`v_2^{\alpha \beta }`$ provided one makes suitable subtractions from $`v_3^{\alpha \beta \gamma }`$ and/or higher-body potentials. Within the GPT, the uniqueness of the potentials is established by ensuring that their desired properties of structure independence and full transferability are consistent with the matrix elements that define them. In this regard, the total energy is normally calculated to second order in the pseudopotential $`W_{kk^{}}`$, so that $`sp`$ contributions enter only in the volume term and the pair potentials. The TM $`d`$-$`d`$ and $`sp`$-$`d`$ contributions to each potential, on the other hand, are carried to all orders in the matrix elements $`\mathrm{\Delta }_{dd^{}}`$, etc. Terms are allocated to pair- and many-body potentials according to how many distinct ionic positions explicitly enter. Thus, for example, the TM pair potentials $`v_2^{TMTM}`$ contain contributions that are even powers of $`\mathrm{\Delta }_{dd^{}}`$ associated with repeated hopping of $`d`$ electrons back and forth between a pair of ions, with the leading term proportional to $`\mathrm{\Delta }_{dd^{}}\mathrm{\Delta }_{d^{}d}`$. The three-ion TM potentials contain corresponding terms of third order proportional to $`\mathrm{\Delta }_{dd^{}}\mathrm{\Delta }_{d^{}d^{\prime \prime }}\mathrm{\Delta }_{d^{\prime \prime }d}`$ and terms of fourth order proportional to $`\mathrm{\Delta }_{dd^{}}^2\mathrm{\Delta }_{d^{}d^{\prime \prime }}^2`$, as well as higher-order terms. The four-ion TM potentials start at fourth order in $`\mathrm{\Delta }_{dd^{}}`$.

The tight-binding-like $`d`$-$`d`$ contributions to the TM potentials are modulated by $`sp`$-$`d`$ hybridization, $`d`$-state nonorthogonality, and other factors such as $`d`$-band filling, but nonetheless, they give valuable insight into the expected short-range behavior of the potentials. In particular, one expects a strong attractive contribution to $`v_2^{TMTM}`$ at short distances resulting from the second-order term in $`\mathrm{\Delta }_{dd^{}}`$. This term is attractive because it directly relates to the second moment of the $`d`$-band density of states and hence to the $`d`$-band width and the additional cohesion provided by partial $`d`$-band filling. The attraction is strong at short distances because the matrix element for atoms separated by distance $`r`$ varies roughly as $`r^5`$, the behavior obtained for pure canonical $`d`$ bands. In addition, one expects this attractive contribution to be maximum near half-filling of the $`d`$ bands and to vanish for completely filled or empty $`d`$ bands. Thus the expected overbinding in $`v_2^{TMTM}`$ will show a clear chemical dependence, with decreasing magnitudes for Co-Co, Co-Ni, and Ni-Ni interactions.

For short-range TM interactions, repulsive contributions from higher-order terms in $`\mathrm{\Delta }_{dd^{}}`$ will balance the attractive contribution of the second-order term in $`v_2^{TMTM}`$, provided that the local concentration of TM atoms is sufficiently high. In general, the detailed balance obtained involves the three-, four-, and possibly higher-ion potentials. Near half-filling of the $`d`$ bands, however, the repulsive contributions will be dominated by the fourth-order terms in $`v_3^{TMTMTM}`$. This in turn suggests a simple scheme to modify the TM pair potentials at short range to incorporate the balance directly, a scheme that we will develop in Sec. III. First, however, we examine the actual calculated GPT pair potentials for the Al-Co-Ni system of interest here.

Figure 1 shows the Al-Al and Al-TM pair potentials for Al-Co-Ni . These are calculated in the aluminum-rich limit, but in practice they do not depend strongly on composition. The first minima of the Al-TM pair potentials occur near 2.3 Å with depths of about 0.2 eV (Al-Ni) and 0.3 eV (Al-Co). Rather than a potential minimum, the Al-Al potential exhibits a shoulder near 3 Å. The TM-TM pair potentials are shown in Fig. 2. As expected, the TM overbinding is most evident for Co. The first minimum in the Co-Co potential has a depth of 2.1 eV at 1.7 Å. The corresponding Ni-Ni potential depth of 0.1 eV at 2.2 Å is not obviously problematic, but in the following we will find it requires some modification. In the present applications, the Co-Ni pair potential $`v_2^{CoNi}`$ is defined as an average of the Co-Co and Ni-Ni potentials,

$$v_2^{CoNi}(v_2^{CoCo}+v_2^{NiNi})/2.$$
(2)
This amounts to a perturbative expansion of $`v_2^{\alpha \beta }`$ in the difference in atomic number $`Z^\alpha Z^\beta `$. Clearly, $`v_2^{CoNi}`$ so-defined suffers overbinding due to the overbinding of $`v_2^{CoCo}`$.

We wish to devise effective pair potentials for Al-Co-Cu and Al-Cu-Ni as well as Al-Co-Ni. Previously, the Al-Cu potentials were found to be well behaved up to large Cu composition , so no modification of $`v_2^{CuCu}`$ is suggested. Our modification to $`v_2^{CoCo}`$ obtained for Al-Co-Ni compounds may be approximately valid for these other compounds. We previously defined  $`v_2^{CoCu}`$ as equal to $`v_2^{NiNi}`$ because Ni lies between Co and Cu in the periodic table. Thus our modified Ni-Ni potential should serve as an approximate modified Co-Cu potential. For the modified Cu-Ni potential we may take $`(v_2^{CuCu}+v_2^{NiNi})/2`$, using the modified Ni-Ni potential. The Al-Co-Cu and Al-Co-Ni potentials so-obtained will, of course, still need to be validated using full ab-initio calculations.

## III Modification of Pair Potentials

As discussed above, the short-ranged attraction in the TM-TM pair potentials is balanced by repulsive terms contained in the three- and higher-body potentials. If one chooses to truncate the GPT expansion at the pair potential level, these repulsive many-body contributions must be “folded” into effective pair potentials. Formally, one may define an effective pair potential by averaging over atomic positions, holding a single pair of ions fixed:

$$v_2^{eff}v_2^{\alpha \beta }+<v_3^{\alpha \beta \gamma }>+<v_4^{\alpha \beta \gamma \delta }>+\mathrm{}.$$
(3)
Such potentials have been previously considered in the context of the simplified model GPT  and canonical $`d`$ bands for central transition metals. There it was found that the four-body interaction oscillates with respect to angles between atoms, with a nearly zero mean, so it does not contribute significantly to $`v_2^{eff}`$. The third-order contribution to $`v_3^{\alpha \beta \gamma }`$ also approximately averages away, but the fourth-order contribution to $`v_3^{\alpha \beta \gamma }`$ contributes strongly, yielding a short-ranged repulsive term proportional to $`\mathrm{\Delta }_{dd^{}}^2\mathrm{\Delta }_{d^{}d}^2r^{20}`$ balancing against the attractive second-order term in $`v_2^{\alpha \beta }`$.

Inspired by the short-ranged repulsion found in Eq. (3) and the power law variation of $`\mathrm{\Delta }_{dd^{}}`$ within the model GPT , we propose to modify the full GPT pair potentials $`v_2^{\alpha \beta }`$ by adding terms of the form

$$U^{\alpha \beta }(r)=a(r_0/r)^b,$$
(4)
where $`a`$ and $`b`$ are positive and depend upon the elements $`\alpha `$ and $`\beta `$ of the pair potential modified. Our expectation, which is confirmed below, is that $`b`$ is large in all cases, so that $`U^{\alpha \beta }`$ is indeed short-ranged. In our applications, the quantity $`r_0`$ is taken as a common atomic separation in quasicrystals of 2.55 Å. Then at a fixed atomic volume and composition the effective pair potential can be written as

$$V^{\alpha \beta }(r)=v_2^{\alpha \beta }(r)+U^{\alpha \beta }(r).$$
(5)
We determine the unknowns $`a`$ and $`b`$ by matching energies and forces obtained from full ab initio electronic-structure calculations on a quasicrystal approximant. Cockayne and Widom  previously suggested a structure for decagonal Al-Co-Cu. An approximant of that structure is shown in Fig. 3 with Ni atoms replacing Cu. The orthorhombic unit cell (a=23.3 Å, b=7.57 Å, c=4.09 Å) contains 50 atoms (Al34Co10Ni6). Most atoms occupy either z=0.25 or z=0.75 layers. Al atoms at the centers of hexagons occupy the z=0.5 layer. Two Co atoms occupy symmetric positions around these central Al atoms. In Al-Co-Cu, alternation of Co and Cu on tile edges is thought to be energetically advantageous . We find that alternation of Co and Ni shown in Fig. 3 is slightly disadvantageous in Al-Co-Ni.

To investigate TM bonding energetics, we alter the basic structure shown in Fig. 3 by swapping a Co atom on a horizontal tile edge (atom b in Fig. 3) with the Ni atom on the other horizontal tile edge (atom c). Focusing on near-neighbor interactions, we find this swap of atoms replaces four Co-Ni bonds with two Co-Co and two Ni-Ni bonds, all of length = 2.55 Å. These numbers are twice as large as is apparent by inspection of Fig. 3, the extra factor of two coming from periodic boundary conditions in the direction perpendicular to the plane.

Now consider the energy change evaluated using pair potentials. Atoms b and c occupy nearly equivalent sites. An exact symmetry in the Al atom positions guarantees that no bond involving an Al atom is affected by the swap. We already noted the change in TM near-neighbor interactions. At further neighbors, with separations of 4.6 Å or greater, we also find interchanges between Co-Co and Ni-Ni bonds for pairs of Co-Ni bonds. If the approximate form (2) of $`v_2^{CoNi}`$ as the average of $`v_2^{CoCo}`$ and $`v_2^{NiNi}`$ were valid, all changes in bonding would exactly cancel each other, resulting in a vanishing energy change. We presume that approximation (2) is more accurate at large separations than small separations. Thus we attribute the entire energy change of the bc swap to near-neighbor energy differences

$$\mathrm{\Delta }E_1=2V^{CoCo}+2V^{NiNi}4V^{CoNi},$$
(6)
where $`V^{\alpha \beta }`$ denotes the strength of the pair potential evaluated at the near-neighbor distance 2.55 Å.

Next we swap one of the Co atoms inside the tiles (atom e) with one of the Ni on a horizontal tile edge (atom a). Two Co-Ni bonds are broken and two Co-Co bonds are produced after this swap. All other interactions that are affected are Al-TM interactions, which we presume to be described accurately by the GPT pair potentials. This swap energy can be written as:

$$\mathrm{\Delta }E_2=2V^{CoCo}2V^{CoNi}+V^{AlTM},$$
(7)
where $`V^{AlTM}`$ represents a calculable collection of interactions between Al atoms and TM atoms at many separations. $`V^{AlTM}`$ should be described accurately by the unmodified GPT pair potentials.

Lastly, we replace the Co-Ni pair on one horizontal tile edge (atoms c and d) with Al atoms. Then we swap one of the newly introduced Al (at position c) with a Ni atom on the other horizontal tile edge (atom a). This breaks two Co-Ni bonds. All other interactions are either Al-TM or Al-Al interactions, and again those are described well within the GPT. The energy change of this swap is

$$\mathrm{\Delta }E_3=2V^{CoNi}+V^{AlTM}+V^{AlAl},$$
(8)
where $`V^{AlAl}`$ and $`V^{AlTM}`$ represent collections of interactions involving Al atoms that, as before, we presume to be accurately calculable within the unmodified GPT.

Full ab initio values for the energy changes $`\mathrm{\Delta }E_1`$, $`\mathrm{\Delta }E_2`$ and $`\mathrm{\Delta }E_3`$ were calculated using VASP (Vienna Ab Initio Simulation Package) . VASP calculates total energies within the local-density approximation using pseudopotentials to treat valence-core electron interactions. We performed calculations using a 4x4x4 k-space grid and also using a 4x4x8 k-space grid to observe the convergence as k-points are added. All calculations were done using medium precision which is expected to be sufficient for our needs. We iterate the self-consistent calculation until an accuracy of $`10^6`$ eV is achieved.

By comparing the energy differences $`\mathrm{\Delta }E_1`$, $`\mathrm{\Delta }E_2`$ and $`\mathrm{\Delta }E_3`$ calculated by VASP with the same quantities calculated with the unmodified GPT potentials, we can obtain the values of $`U^{\alpha \beta }`$ evaluated at the near-neighbor separation 2.55 Å. Specifically, when energy changes calculated by the unmodified GPT are subtracted from energy changes calculated by VASP, assuming that the contributions $`V^{AlAl}`$ and $`V^{AlTM}`$ are accurately calculated with the unmodified GPT, we find

$`\mathrm{\Delta }E_1^{VASP}\mathrm{\Delta }E_1^{GPT}=2U^{CoCo}+2U^{NiNi}4U^{CoNi}`$ (9)
$`\mathrm{\Delta }E_2^{VASP}\mathrm{\Delta }E_2^{GPT}=2U^{CoCo}2U^{NiNi}`$ (10)
$`\mathrm{\Delta }E_3^{VASP}\mathrm{\Delta }E_3^{GPT}=2U^{CoNi}.`$ (11)
Since each correction $`U^{\alpha \beta }(r)`$ involves two unknowns, $`a`$ and $`b`$, Eq. (9) consists of three equations in six unknowns. Additional information is obtained from the forces on atoms calculated by VASP. By examining the forces on the Co-Ni pair (atoms c and d) in Fig. 3, and on the Co-Co and Ni-Ni pairs created by the bc swap, we obtain three additional equations governing the derivatives of $`U^{\alpha \beta }`$ at the near-neighbor separation. This additional information allows closure of the equations and determination of the unknowns.

## IV Results

Table I shows the energy differences $`\mathrm{\Delta }E_i`$ in Eqs. (6)-(8) calculated using GPT pair potentials and VASP. Comparing the VASP data for the two grid sizes, we note that the signs and approximate magnitudes of $`\mathrm{\Delta }E_i`$ are consistent with each other. One immediate result from Table I is that mixed Co-Ni bonds are disfavored over pure Co-Co and Ni-Ni bonds. The energy difference $`\mathrm{\Delta }E_1`$ results from breaking four Co-Ni bonds and producing two Co-Co and two Ni-Ni bonds. $`\mathrm{\Delta }E_1`$ calculated by VASP is negative, showing that the swap lowers the system energy. This means that for Al-Co-Ni, similar TM atoms prefer to reside near each other on the tile edges. Cockayne and Widom found the opposite for the case of Al-Cu-Co using mock ternary potentials , and this was confirmed later using a full ab-initio technique .

Also concerning the calculated values of $`\mathrm{\Delta }E_1`$, we see that the averaged potential approximation (2) is fairly accurate. GPT yields $`\mathrm{\Delta }E_1=0`$ because it employs this approximation here. The small value of $`\mathrm{\Delta }E_1`$ obtained by VASP confirms that this approximation is not far off the mark.

Figure 4 shows the x-component of the total force on certain TM atoms. Our (4x4x4) and (4x4x8) VASP calculations yield forces that agree to 0.06 eV/Å or better. We examine the horizontal bonds ab and cd in Fig. 3 in both the original and swapped configurations. As expected, at 2.55 Å, GPT pair potentials predict attractive forces between TM pairs while the actual forces obtained from VASP are repulsive. The small force asymmetry on atoms in the Co-Ni pair is due to the different ways Co and Ni atoms interact with their surrounding environments. The difference between the forces calculated by our two methods is greatest for Co-Co bonds and smallest for Ni-Ni bonds, consistent with our expectation that overbinding is more severe for Co than for Ni.

Calculated modifications to the GPT pair potentials are given in Table II. Examining the magnitude of $`U^{\alpha \beta }`$ at $`r`$=$`r_0`$=2.55 Å (i.e., the value of $`a`$), we note that $`U^{NiNi}`$ is smaller than $`U^{CoCo}`$, as is expected since Ni is closer to the end of the $`3d`$ transition series, with its $`d`$-bands almost full. It should be noted that $`r`$=2.55 Å is not the potential minimum. It is rather the nearest-neighbor distance at which the calculations were performed. The quantities $`V^{\alpha \beta }`$ and $`F^{\alpha \beta }`$ are, respectively, the energy and force calculated from the modified GPT potentials \[Eq.( 5)\] at the near-neighbor distance $`r_0`$. The large values of $`b`$ we obtain show that our modifications of the GPT pair potentials fall off rapidly beyond the near-neighbor separation and confirm our expectations based on Eq. (3). The modified potentials are illustrated in Fig. 5. The (4x4x4) and (4x4x8) VASP calculations agree in positions of the potential minima to about 0.05 Å and agree in the values at the minima to about 0.02 eV.

## V Discussion

The original GPT interatomic potentials were derived from first principles without reference to specific structures. Their applicability to, and transferability among, a broad range of structures was verified . The pair potentials alone apply to Al-rich structures in which TM atoms are well separated, but fail due to an unphysical short-ranged TM attraction. Our modification of the GPT potentials is restricted to TM pair potentials. Since the correction $`U^{\alpha \beta }(r)`$ is negligible beyond 3 Å, our corrections only affect energies and forces among neighboring TM atoms.

In idealized decagonal AlNiCo and AlCuCo quasicrystal models, neighboring TM atoms always occur in specific atomic environments consisting of zig-zag chains of TM atoms at 2.5 Å spacing surrounded by Al atoms at special positions . A variety of quasicrystal and approximant structures differ in the arrangement of these chains in space, but share the same local structure around the TM atoms. Our modified GPT potentials are therefore strictly transferable within this class of quasicrystal structures.

While the modified GPT potentials are not strictly transferable outside this special class of structures, we do believe they are qualitatively transferable. Comparing figures 2 and 5, we have replaced obviously unphysical pair potentials with a set that appears qualitatively realistic. Both original and modified pair potentials are transferable among structures without TM neighbors. The modified pair potentials provide a reasonable, though non-rigorous, extension to structures with TM neighbors.

As a test of our modified pair potentials, we relaxed the basic structure using both original and modified GPT pair potentials, and using VASP. In all three runs we relaxed the structure until all atomic forces were less than 0.001 eV/Å. Under VASP relaxation (4$`\times `$ 4$`\times `$4 k-space grid), Al atoms moved 0.19 Å on average, followed by Ni with an average displacement of 0.16 Å and Co with an average displacement of 0.15 Å. Relaxation under the modified GPT potentials produced a structure close to the VASP relaxed structure. The differences between modified GPT and VASP relaxed positions are less than 0.07 Å for every TM atom, with an average difference of 0.05 Å/TM atom. In contrast, relaxation under the original GPT pair potentials yielded a maximum TM relaxed position difference of 0.20 Å and an average TM difference of 0.13 Å.

As a result of our modifications, the TM atoms relax in the correct directions and move approximately the correct distances. This is not the case using the original GPT potentials. Since TM separations move away from $`r_0`$ under relaxation, our proper behavior under relaxation demonstrates a type of transferability of the potentials.

###### Acknowledgements.

IA wishes to thank King Abdul Aziz University (Saudi Arabia) for supporting his study and MW acknowledges support by the National Science Foundation under grant DMR-9732567. The work of the JAM was performed under the auspices of the U. S. Department of Energy at the Lawrence Livermore National Laboratory under contract number W-7405-ENG-48. VASP calculations were performed at the Pittsburgh Supercomputer Center and at NERSC.


format: text

text:
# 1 Introduction

## 1 Introduction

Young stars are good tracers of the galactic spiral structure in the solar neighbourhood, but, unfortunately, the observational data available up to now have not allowed to reach conclusive results on the parameters describing such structure. The accurate astrometric data provided by Hipparcos (ESA 1997) allow us to re-examine the kinematic behaviour of these stars and, even more, to evaluate the possibility to undertake this study using more sophisticated kinematic models.

In a previous paper (Torra et al. 2000) we characterized the structure and kinematics of the Gould Belt system, establishing its boundary to a distance of 600 pc from the Sun. Beyond this distance, the kinematic behaviour of young stars, in particular O-B stars and Cepheids, has to reflect the smooth galactic potential, that is the galactic rotation and the kinematics owing to the spiral structure. The study of the stellar velocity field outside the Gould Belt is undertaken in the present paper, considering both the current observational material – its errors and the sample’s constraints – and, through realistic simulations, the robustness of the resolution process. In particular, for Cepheid stars, the influence of the period-luminosity relation (PLR) on the derived kinematic parameters is also evaluated.

## 2 The working samples

### 2.1 Sample of O- and B-type stars

The construction of this sample using Hipparcos data is fully described in Fernández (1998) and Torra et al. (2000). Due to the uncertainty on trigonometric parallax at large distances, these were computed following Crawford’s (1978) photometric calibration. Preliminary results applying the LM method (Luri et al. 1996) to Hipparcos data indicate this calibration is good enough for our purposes (Jordi et al. 2000). Considering only those stars with an heliocentric distance 0.6 $`<R<`$ 2 kpc, the sample with distances and proper motions contains 444 stars, whereas the subsample with available radial velocities (Grenier 1997) contains 304 stars.

### 2.2 Sample of Cepheid stars

The initial sample contains all the Hipparcos classical Cepheids. Astrometric data were taken from this catalogue and radial velocities from Pont et al. (1994, 1997). Two PLR have been used for distance computation: Luri’s (1999) relation, which corresponds to the short cosmic distance scale ($`M_v=1.082.72\mathrm{log}P`$), and Feast & Catchpole (1997) relation, which gives a long cosmic scale ($`M_v=1.412.81\mathrm{log}P`$). In both cases, periods were obtained from Hipparcos and individual reddenings from Fernie et al.’s (1995) compilation (continuous updating). Up to $`R=`$ 4 kpc, the sample with known distances and proper motions contains 203 stars and the subsample with known radial velocities contains 179 stars.

## 3 Kinematic model

Our kinematic model considers the systematic contributions of solar motion, differential galactic rotation (up to second-order approximation) and spiral arm kinematics (modeled in the frame of the Lin’s theory). In addition to the solar motion, we derived the first- and second-order terms of the galactic rotation curve, the phase of the spiral structure at the Sun’s position, the amplitudes in the perturbation of the velocity in the galactocentric and tangential directions and an adimensional parameter which takes into account the difference in the velocity dispersion between the solar-type stars and the considered stars. There are four free parameters: the number of spiral arms of the galaxy ($`m`$), their pitch angle ($`i`$), the galactocentric distance of the Sun ($`\varpi _{}`$) and the circular velocity at the Sun’s position ($`\mathrm{\Theta }(\varpi _{})`$). A couple of values of these parameters were considered: $`m=`$ 2 or 4, $`i=6^{}`$ or $`12^{}`$, $`\varpi _{}=`$ 7.1 or 8.5 kpc and $`\mathrm{\Theta }(\varpi _{})=`$ 184 or 220 km s-1. The kinematic parameters were derived via weighted least squares fit, following an iterative scheme. Three cases were studied, solving the equations considering only radial velocities, only proper motions and the combined resolution (see Fernández et al. 2001).

## 4 Test of robustness: simulations

Numerical simulations were performed in order to quantitatively evaluate the biases in the kinematic model parameters induced by, among others, the observational errors, the incompleteness of the sample, the rejection of high residual stars and the correlations among the parameters. Both O-B star and Cepheid samples were simulated considering the same spatial distribution than the real sample and a Schwarzschild distribution for the residual velocities. Solar motion, galactic rotation and spiral arm kinematics were introduced following our kinematic model. We assumed gaussian errors in distance, radial velocity and proper motions.

Detailed conclusions of these simulations can be found in Fernández et al. (2001). As main results, we conclude that the combined solution minimizes the biases induced by correlations. The observational errors in proper motion, radial velocities and distance produce biases less than 0.5 km s-1 in the solar motion components and in the galactic rotation and spiral structure parameters. Due to the spatial distribution of the available data, the best distance intervals were found to be 0.6 $`<R<`$ 2 kpc for O-B stars and $`R<`$ 4 kpc for Cepheids.

## 5 Results and discussion

### 5.1 Galactic rotation curve

For the $`A`$ Oort constant, a discrepancy between the different solutions has been found: $`A^{\mathrm{O}B}13.6\pm 0.7`$ km s-1 kpc-1 for O-B stars and $`A_{\mathrm{L}uri}^{\mathrm{C}ep}16.7\pm 0.6`$ km s-1 kpc-1, $`A_{\mathrm{F}east}^{\mathrm{C}ep}15.0\pm 0.6`$ km s-1 kpc-1 for Cepheids (Luri’s 1999 and Feast & Catchpole’s 1997 PLRs, respectively). This discrepancy has been extensively found in the literature (e.g. Hanson 1987, Metzger et al. 1997, Feast & Whitelock 1997 and Mishurov & Zenina 1999 obtained values between 11.3 and 18.8 km s-1 kpc-1) and, as pointed out by Olling & Merrifield (1998), it can be produced by the different spatial distribution of the samples. In agreement with Feast et al. (1998), we found a very small second-order term of the galactic rotation, compatible with a linear rotation curve in the solar neighbourhood.

### 5.2 Galactic spiral structure

Using both O-B and Cepheid stars data, we found an angular rotation velocity for the spiral pattern of $`\mathrm{\Omega }_\mathrm{p}`$ 30-35 km s-1 kpc-1, incompatible with the classical value 13.5 km s-1 kpc-1 proposed by Lin and collaborators in the later 60s. Our value is in good agreement with the larger values recently published by Amaral & Lépine (1997) and Mishurov et al. (1997, 1999). From this value we can conclude that the Sun is outside – though near – the corotation circle.

From the available data we are not able to decide on a galaxy with 2 or 4 spiral arms. Nowadays, this is an unsolved problem (see contradictory results in Amaral & Lépine 1997, Mishurov & Zenina 1999, Drimel 2000, Lépine et al. 2000). Nevertheless, good coherence is obtained to derive the phase of the spiral structure: from both samples, we obtained values in the rank , indicating the Sun is near the potential minimum of an arm. The values of the velocity amplitudes due to the spiral perturbation were found to be small, about 2 km s-1.

###### Acknowledgements.

This work has been suported by the CICYT under contracts ESP97-1803 and ESP1999-1519-E.


text:
# Thermal Magnetization Reversal in Arrays of Nanoparticles

## Abstract

The results of large-scale simulations investigating the dynamics of magnetization reversal in arrays of single-domain nanomagnets after a rapid reversal of the applied field at nonzero temperature are presented. The numerical micromagnetic approach uses the Landau-Lifshitz-Gilbert equation including contributions from thermal fluctuations and long-range dipole-dipole demagnetizing effects implemented using a fast-multipole expansion. The individual model nanomagnets are $`9\mathrm{nm}\times 9\mathrm{nm}\times 150\mathrm{nm}`$ iron pillars similar to those fabricated on a surface with STM-assisted chemical vapor deposition \[S. Wirth, et al., J. Appl. Phys 85, 5249 (1999)\]. Nanomagnets oriented perpendicular to the surface and spaced $`300\mathrm{nm}`$ apart in linear arrays are considered. The applied field is always oriented perpendicular to the surface. When the magnitude of the applied field is less than the coercive value, about $`2000\mathrm{Oe}`$ for an individual nanomagnet, magnetization reversal in the nanomagnets can only occur by thermally activated processes. Even though the interaction from the dipole moment of neighboring magnets in this geometry is only about $`1\mathrm{Oe}`$, less than $`1\%`$ of the coercive field, it can have a large impact on the switching dynamics. What determines the height of the free-energy barrier is the difference between the coercive and applied fields, and $`1\mathrm{Oe}`$ can be a significant fraction of that. The magnetic orientations of the neighbors are seen to change the behavior of the nanomagnets in the array significantly.

The ability of the magnetization to maintain one particular orientation among many is an essential part of numerous applications of magnetic materials. The coercive field is defined to be the weakest magnetic field for which the magnetization will deterministically align with the field. For applied magnetic fields weaker than the coercive field, a free-energy barrier may separate the orientation of the magnetization from that of the applied magnetic field. In these weak fields the changes in the orientation of the magnetization occur only in the unlikely event of thermal crossing of the free-energy barrier, and magnetization switching becomes a probabilistic process. In magnetic storage, thermal magnetization switching is important for understanding the reliability of recorded data in the presence of stray fields, as well as for thermally assisted reading and writing.

Here we present numerical results for magnetization switching in linear arrays of weakly coupled nanoscale magnetic pillars, with each pillar’s long axis oriented in the $`z`$-direction, perpendicular to the substrate. The simulations start at $`t`$$`=`$$`0.25\mathrm{ns}`$ with zero external field and the average $`z`$-component of the magnetization, $`M_z,`$ oriented in the positive $`z`$-direction. The external field is then applied according to $`H_z(t)=H_0\mathrm{cos}(2\pi t/1\mathrm{ns})`$ for $`0.25\mathrm{ns}<t<0\mathrm{ns},`$ giving a final value of $`H_0.`$

The single-crystal nanomagnet pillars considered here are modeled after iron nanopillars constructed using STM-assisted chemical vapor deposition.  The numerical model consists of magnetization vectors of magnitude unity on a cubic lattice, $`𝐌(𝐫_i)`$, with the motion of the vectors given by the Landau-Lifshitz-Gilbert equation,

$$\frac{d𝐌(𝐫_i)}{dt}=\frac{\gamma _0}{1+\alpha ^2}𝐌(𝐫_i)\times \left[𝐇(𝐫_i)\alpha 𝐌(𝐫_i)\times 𝐇(𝐫_i)\right],$$
(1)
where $`\gamma _0`$ is the gyromagnetic ratio $`1.76\times 10^7\mathrm{Hz}/\mathrm{Oe}`$ and $`𝐇(𝐫_i)`$ is the local field at each site. The local fields have contributions corresponding to exchange, dipole-dipole interactions, and random thermal noise. Underdamped precession of the spins is selected by taking the damping parameter $`\alpha =0.1`$; the other material parameters were chosen to match those of bulk iron, and are $`3.6\mathrm{nm}`$ for the exchange length, $`1700\mathrm{emu}/\mathrm{cm}^3`$ for the saturation magnetization, and zero crystalline anisotropy. Details of the numerical model will appear in Ref. . Two numerical models of the nanopillars are considered: a large-scale simulation with each pillar modeled with $`4949`$ vectors and a simpler model with each pillar modeled with only $`17`$ vectors.

The large-scale simulations model each $`9\mathrm{nm}\times 9\mathrm{nm}\times 150\mathrm{nm}`$ pillar using a $`7`$ $`\times `$ $`7`$ $`\times `$ $`101`$ lattice. For these simulations, the time-consuming dipole-dipole calculations were performed using the fast-multipole method,  and the simulations were run on a series of massively parallel computers including a CRAY T3E and two different IBM SP’s. The results reported here represent $`10^5`$ cpu-hours of computation. The pillars were separated by twice their length, or $`300\mathrm{nm}.`$ At this separation the interactions between neighboring iron pillars are on the order of $`1\mathrm{Oe}.`$

Here we consider linear arrays of nanopillars, $`4\times 1`$ arrays in which there are two classes of pillars, which we call “inside” and “outside.” The switching time for each pillar is taken to be the first time the value of $`M_z`$ for that pillar passes through zero, and it is measured from $`t`$$`=`$$`0`$. The results are presented in Fig. 1 as $`P_{\mathrm{not}}(t),`$ the probability that a pillar has not switched up to time $`t.`$ A total of $`30`$ array switches, thus $`60`$ for each class of pillar, were simulated for $`H_0`$$`=`$$`1800\mathrm{Oe}`$ and $`T`$$`=`$$`20\mathrm{K},`$ and the results are compared to $`100`$ switches simulated for isolated pillars under the same conditions.  The field magnitude used here is below the coercive field for isolated nanoparticles, which has been estimated to be $`1995\pm 20\mathrm{Oe}`$ in dynamic, nonequilibrium simulations where the field is swept linearly.  From these results it appears that the outside pillars switch, on average, at earlier times than either the inside pillars of the array or the isolated pillars. We note that functional forms for $`P_{\mathrm{not}}(t)`$ that are neither exponentials nor the error functions associated with Gaussian statistics have been observed experimentally.  A simple theory with an analytic form for $`P_{\mathrm{not}}`$ reasonably describes the simulation results for isolated pillars.

To investigate switching involving much larger free-energy barriers, and thus longer switching times, simulations were also conducted with a simplified model of the pillars, specifically with each pillar modeled by a $`1`$ $`\times `$ $`1`$ $`\times `$ $`17`$ arrangement of magnetization vectors.  This models a $`5.2\mathrm{nm}\times 5.2\mathrm{nm}\times 88.4\mathrm{nm}`$ iron pillar, which has approximately the same aspect ratio as the previous pillar. For an isolated pillar of this type, the coercive field is approximately $`1500\mathrm{Oe}.`$ The pillars in these arrays were separated by $`176.8\mathrm{nm},`$ and the dipole-dipole interactions were calculated using direct summation.  Because this approach is $`O(N^2)`$ the calculation, which is fast for individual pillars, is slow for even small arrays. Still, these simulations are computationally less expensive than those discussed above, and results are presented for $`1269`$ array switches and $`1986`$ isolated pillar switches. The results reported here required about $`10^4`$ cpu-hours of computation on desktop workstations.

The $`P_{\mathrm{not}}(t)`$ for $`4\times 1`$ arrays of the simple model with $`H_0=1000\mathrm{Oe}`$ and $`T=20\mathrm{K}`$ are shown in Fig. 2, along with the results for isolated pillars under the same conditions. In this case, the differences in $`P_{\mathrm{not}}(t)`$ are small, but the array pillars still appear to have a small bias to switch at earlier times than isolated pillars. Under these conditions, however, the effect of the magnetic orientation of the nearest-neighbor pillars can be seen. Fig. 3 shows subsets of $`P_{\mathrm{not}}(t)`$ for the switching of inside pillars in the simple model. The dotted and dashed curves are $`P_{\mathrm{not}}`$ for inside pillars where one and both nearest-neighbor pillars have already switched, respectively. Here the switching time is measured from the last time one of the nearest-neighbor pillars switched. The data is presented on a linear-log scale, and in both cases $`P_{\mathrm{not}}`$ is consistent with an exponential form. This suggests that pillars in these environments have an approximately constant, history-independent decay rate determined by the orientation of the nearest-neighbor pillars. The exponential form is consistent with our simple theory for $`P_{\mathrm{not}}`$ in nanomagnet pillars,  because environments with switched neighbors cannot exist for times less than $`t_\mathrm{g},`$ the growth time from nucleation of one endcap to $`M_z`$ passing through zero. The solid curve is $`P_{\mathrm{not}}`$ constructed from the data for pillars with two neighbors, neither of which have switched. The $`t_{\mathrm{sw}}`$ used for this data occur at times greater than $`t_g,`$ here estimated using our simple theory  as twice the earliest observed $`t_{\mathrm{sw}}.`$ In addition $`t_g`$ has been subtracted from each $`t_{\mathrm{sw}}`$ for this curve. Similar results for the outside pillars of the array are shown in the inset of Fig. 3. The trend towards slower decay with increasing number of switched neighbors is consistent with a simple picture of dipole-dipole interaction between nearest-neighbor pillars with an unswitched neighbor contributing a field parallel to the external field and a switched neighbor contributing a field antiparallel to the external field. Currently, a sufficient number of samples do not exist to reliably repeat this analysis for the larger simulations.

To summarize, we have simulated the switching dynamics in linear arrays of nanomagnet pillars after a reorientation of the external field, both for a simple model in which each pillar is represented by a one-dimensional array of magnetization vectors and for a large-scale model with each pillar represented by a three-dimensional lattice of vectors. In one-dimensional arrays of pillars that are mutually located in the other pillars’ far fields and that have small free-energy barriers, the $`P_{\mathrm{not}}(t)`$ of the pillars at the end of the arrays falls off faster than that of isolated pillars and the inside pillars of the array. For pillars that have large free-energy barriers, the long switching-time tails of $`P_{\mathrm{not}}`$ for pillars with different numbers of switched nearest neighbors show exponential behavior, with decay constants that decrease with increasing numbers of switched neighbors. This occurs because the presence of unswitched (switched) neighbors enhances (retards) switching.

Supported by NSF grant No. DMR-9871455, NERSC, and by FSU/CSIT, FSU/MARTECH, and FSU/ACNS.


text:
# Quantum atomistic solid-state theory

## Abstract

Postulates of the quantum atomistic solid-state theory (QUASST) have been presented. QUASST is an extension of the crystal-field theory and is applicable to compounds containing open-shell 3d, 4f and 5f atoms. QUASST points out the existence in a solid of the atomic-like discrete electronic structure determined by the crystal-field and spin-orbit interactions. This approach unifies the description of 3d and 4f ions and allows to bridge the atomic physics and the solid-state physics.

The aim of the quantum atomistic solid-state theory (QUASST) is the consistent physical model for the understanding of electronic, magnetic (e-m) and spectroscopic properties of systems containing atoms with an incomplete electronic shell, namely 4f, 3d and 5f shells. Surely at present most evidence for the physical adequateness of QUASST exists for rare-earth systems - we are quite convinced about the substantial applicability of QUASST to 3d- and 5f-atom compounds. In presenting QUASST we will concentrate on 4f-atom compounds but the same holds for 5f- and 3d-atom compounds. Among different properties we can mention the magnetic moment, the value and its direction at 0 K and at ambient temperatures, temperature dependence of the heat capacity and the paramagnetic susceptibility, the anisotropy of magnetic properties. Surely we are interested in the energy spectrum of available electronic states and their nature. Surely we think about the formation of the magnetic moment, its spin and orbital contributions, as well as a symmetry breaking during the formation of the magnetic state.

QUASST accepts a picture called sometimes ionic, but we have to say that, according to us, this ionic model never was clearly formulated. Even, when it is sometimes used it is very often misleadingly used, in particular in case of 3d ions.

The basic ideas of the CEF theory (put forward by Bethe in 1929) - the existence of the discrete energy states for the paramagnetic open-shell 4f ions and the importance of the local symmetry - is taken as the main ingredients in the construction of the more general theory for the solids - the quantum atomistic solid-state theory. The basic idea of QUASST is that i) the paramagnetic atoms preserve much of their atomic properties also being the part of a solid. Otherwords - 4f/3d/5f atoms exist also in a solid. The novelty of this simple idea can be understood if one remembers that in the presently-in-fashion modern theories of solids atoms somewhere disappear. It is clearly visible in the band theories, more often recently used for the description of systems with open-shell atoms, that yield the continuous energy spectrum.

We should explain that in different compounds different ionic states of the paramagnetic atom can be formed. Pr is, for instance, trivalent in Pr2O3, PrAl2 and in PrNi5 but is tetravalent in PrO2. The different ionic states we consider as different states of the atom. The good description of PrNi5 and ErNi5 , that are intermetallics, indicates that there exists the Pr3+ and Er3+ ions despite of the conduction band electrons. It means, that we can have the clearly defined ionic state, with the well-defined integer number of 4f electrons, in an intermetallic compound. Then, apart of the description of the Pr3+ ions we should discuss properties of conduction electrons. In RENi5 their contribution to the heat capacity and to the paramagnetic susceptibility is small and is the trivial function of temperature. Similarly the Co atom in CoO is in the divalent state but it is in the trivalent state in LaCoO3.

By the preservation of the atomic structure we understand that the Pr3+ ion, for instance, has the atomic-like 4f2 system (other electrons are in close shells). It means that the intra-atomic interactions are strong enough to preserve this highly-correlated electronic system also when atom is the part of a solid and undergoes interactions with surroundings. Similarly six 3d electrons of the Co3+ ion form the highly-correlated 3d6 electronic system. Thus ii) n 4f/3d/5f electrons form the highly-correlated 4fn/3dn/5fn electronic system. Subsequently we have the term and multiplet structure known from the atomic physics. The intra-atomic correlations lead to iii) the ground term of the 4fn/3dn/5fn system with the resultant S and L given by Hund’s rules. Then we work in the (2S+1)(L+1) space. In case of 4f and 5f ions this space is further reduced (by the existence of the large spin-orbit coupling) to the (2J+1) space, where J of the lowest multiplet is given by the 3rd Hund’s rule.

QUASST points out iv) the importance of the intra-atomic spin-orbit (s-o) coupling. So far the 4f ions are described within the large s-o limit whereas the s-o coupling has been largely ignored for 3d ions. There is the time to take into account the finite, though quite large, for the s-o coupling in description of rare-earth ions and the non-zero, though relatively weak, s-o coupling for the 3d ions. It turns out that the large s-o limit used in the description of rare-earth ions is quite physically adequate - it means that taking into account the finite s-o coupling does not introduce the revolution in the low-energy part of the electronic structure, but allows to explain, for instance, the appearance of the higher multiplets at the finite energies (the excited multiplet for the Sm3+ ion lies at 120 meV only as detected by inelastic-neutron-scattering experiments of Furrer et al. ). However, in case of the 3d ions taking into account the s-o coupling, even of the small value, causes the completely new low-energy electronic structure  and dramatically changes the shape of eigenfunctions in comparison to the situation with $`\lambda _{so}`$ = 0. In fact, the smaller value of the s-o coupling the lower energy scale in the electronic structure appears and the lower temperature range, where anomalies of electronic and magnetic properties appear.

QUASST points out v) the existence of the discrete electronic structure associated with the atomic-like states of the 4fn/3dn/5fn systems in a solid.

QUASST points out vi) the importance of the atomic scale symmetry on the electronic structure, in particular on the realized ground state and its magnetic moment, both the value and the direction. This electronic structure determines the electronic and magnetic properties macroscopically observed both at zero temperature as well as at ambient temperatures.

QUASST points out vii) the strong interplay of the magnetic state of a paramagnetic ion and the symmetry of the electric field produced by surrounding charges. The electric field produced by surrounding charges within the CEF community is known as the crystal field. The well-known example is the Pr3+ ion in PrNi5. It is the local symmetry of the crystal field that produces the non-magnetic state of the paramagnetic ion. Within the CEF community this effect is discussed in the connection to the Kramers and the Jahn-Teller theorem. The CEF interactions can substantially reduce the local magnetic moment also in case of the Kramers ions. It has been found that the hexagonal symmetry CEF can produce a non-magnetic Kramers-doublet ground state for the highly-correlated f3 system . Recently we have shown  that the long-time intriguing non-magnetic state of LaCoO3 is due to the non-magnetic state of the Co3+ ion. This non-magnetic state is produced in the atomic scale by the trigonal off-cubic distortion provided the intra-atomic spin-orbit coupling is taken into account. It has been also shown that viii) for the 3d-ion compounds the Jahn-Teller theorem has to be considered within the spin-orbital space in contrary to the orbital-only space considered so far. Such the treatment makes unification with the rare-earth ions where we customarily consider the Jahn-Teller theorem within the spin-orbital space. In fact, such the treatment came to the rare-earth magnetism in a very natural way with the acceptance after the works of Hund (1925) and Van Vleck (1929, 1932) that J is the good quantum number for 4f ions. Simultaneously the works of Van Vleck (1932), Schlapp and Penney (1932) have introduced the quenching of the orbital moment in the 3d ions that gave a start for the (erroneous) consideration of 3d-ion magnetism as related with the spin-only moment.

QUASST, providing the discrete electronic structure, ix) enables the calculation of whole thermodynamics. The obtained temperature dependences of the heat capacity and the paramagnetic susceptibility are in remarkably good agreement with experimental data for continuously increasing great number of compounds \[1, 2, 7-12\].

QUASST points out x) the multipolar character of the electric field existing in a solid. The higher-order CEF interactions are very important. Higher-order CEF parameters reflect multipolar charge interactions. The parameters B$`{}_{}{}^{n}{}_{2}{}^{}`$, B$`{}_{}{}^{n}{}_{4}{}^{}`$ and B$`{}_{}{}^{n}{}_{6}{}^{}`$, for instance, are associated with the quadrupolar, octupolar and hexadekapolar interactions, respectively, and all of them have enormous influence on the realized electronic structure. Note, that their influence cannot be treated as the subsequent expansion terms.

QUASST xi) distinguishes the atomic-like properties of the single ion and the macroscopic properties. In the simplest case the molar heat capacity is obtained from the single-ion heat capacity by multiplying by the Avogadro number. The same holds for the paramagnetic susceptibility and the ordered magnetic moment. This is justified only in case of the simplest structures. In general, there can be in the crystal structure a few non-equivalent sites with the different lattice point symmetry. However, the further site differentiation can occur by the symmetry of the local crystal field. The principal axis of the electric field gradient can differ from site to site forming, for instance, the zig-zag structure. As the symmetry can be very low the principal axis of the quadrupolar (B$`{}_{}{}^{m}{}_{2}{}^{}`$), octupolar (B$`{}_{}{}^{m}{}_{4}{}^{}`$) and hexadekapolar (B$`{}_{}{}^{m}{}_{6}{}^{}`$) interactions is necessary to consider too. It makes the direct correlation between the atomic-like properties and macroscopic properties not always straightford.

QUASST postulates xii) the lowering symmetry with the lowering temperature as much as possible as the general rule (the extension of the Jahn-Teller theorem). It causes that with the lowering temperatures we should take into account more and more inequivalent sites what makes the CEF and QUASST calculations much more troublesome.

xiii) The magnetic state is related with the time-reversal symmetry (TRS) breaking that can be traced by the TRS breaking at the atomic scale as the Zeeman-like effect \[1, 2, 8-10\]. The nicest illustration for it is the splitting of the Kramers doublet ground state. The formation of the magnetic state is somehow forced by the lowering-energy demand - this lowering energy is nicely visible even in the atomic scale in case the Kramers doublet ground state. In case of a non-Kramers system the existence of a closely-lying localized state helps in the formation of the magnetic state.

xiv) Energies involved in the formation of the magnetic state are relatively weak. For NiO with TN of 525 K the energy gain amounts to 3.25 kJ/mol (=33.5 meV/ion) . It is much smaller than the Stoner splitting I, that is of order of 0.6-1.2 eV.

xv) The molecular field Bmol is quite small. In case of NiO Bmol amounts to 510 T  and the effect of this field is visible in the atomic-like discrete electronic structure.

QUASST makes the unification in the theoretical description of the 3d and 4f ions.

QUASST makes the unification in the theoretical description of the 5f- and 4f- ion compounds. Very good description of electronic, magnetic and spectroscopic properties of UPd2Al3 , UGa2 , NpGa2  and NpPd2Al3 have been described within the CEF theory with the trivalent state of the actinide ions. The remarkably good applicability is really surprise knowing that all of these compounds are metallic. Moreover, UPd2Al3 exhibits at low temperatures superconductivity and the heavy-fermion behavior.

QUASST starts the discussion of the correlation among the d and f electrons from the highly-correlated limit.

QUASST starts the description of a solid from the description of the involved atoms.

QUASST bridges the atomic physics and the solid-state physics.

One can ask: ”Is this atomic idea a new one in the solid-state physics?” Yes and no. No, as most of experimentalists naturally discuss their results in terms of local properties. Yes, as according to our knowledge noone has been able to resist to presently-in-fashion solid-state physics theories that simply ignore the existence of the atom in the solid arguing that the solid is so many-body object and that there are so strong intersite correlations that the individuality of atoms is lost. In the standard band-structure calculations the f and d electrons are taken as itinerant forming a band. In the band there is a continuum of the energy states within 1-5 eV. In our model there are discrete states with energy separations even less than 1000 times smaller (1 meV, but 0 in case of Kramers ions). No, as there are some text books written about the crystal field, let mention a book of Abragam and Bleaney  or Ballhausen . Yes, as they applied the CEF approach to some diluted 3d systems, not to the concentrated ones. Yes, as they have not been consequent enough and by discussing different crystal-field approaches (weak, strong, …) with further concepts (e.g. low- and high-spin states) they largely washed up the original idea. Please note that in the strong CEF approach the n 3d electrons are treated as largely independent, i.e. they do not form the highly-correlated 3dn system in contrary to the present model. Our approach corresponds to the weak crystal-field approach, but we point out the fundamental importance of the intra-atomic spin-orbit coupling, despite of its relative weakness for the 3d ions. Also yes, as at present this atomic-like picture is enormously prohibited in the leading physical journals and a little is said about the discrete states in the magnetic and strongly-correlated electron system conferences.

We would like to add, preceding unfounded critics, that we do not claim that everything can be explained only by single atoms but our point is that the proper, i.e. physically adequate starting point for the discussion of properties of the solid containing the open-shell atoms is the consideration of its atomic states. Our numerous computer experiments point out that e.g. the orbital moment has to be unquenched in the solid-state physics of 3d-ion containing compounds and our approach enables it. For instance, we have derived the orbital moment in NiO to be 0.54 $`\mu _B`$ what amounts to 20 % of the total moment (2.53 $`\mu _B`$) . Moreover, one should not consider our approach as the treatment of an isolated atom - we start the discussion of NiO from the consideration of the cation octahedra NiO6 (more exactly \- the Ni2+ ion in the octahedral crystal field). The whole NaCl structure of NiO is built up from the edge sharing cation octahedra. The perovskite structure, for instance, is built up from the corner (and the edge) sharing cation octahedra along the c direction (in the a-b plane). Thus, such octahedra cover the whole macroscopic sample provided the perfect translational symmetry. The CEF parameters contain information about the interaction of the single ion with the whole charge surroundings. Our approach is in agreement with the general conviction about the importance of the electron correlations in description of open-shell compounds - in our approach we start from the very highly-correlated limit in contrary to a weak correlation limit of the LSDA approach.

In conclusion, on basis of the extended analysis of experimental results for the great number of compounds containing 4f, 5f and 3d open-shell atoms we have developed the quantum atomistic solid-state theory. This theory points out the existence of the discrete electronic structure associated with atomic-like states of the involved 4f, 3d, 5f atoms. The existence of such the structure causes dramatic changes of the low-temperature electronic and magnetic properties like the formation (or not) of the local magnetic moment and its long-range magnetic order, temperature dependence of the magnetic susceptibility and of the heat capacity and according to us most of the experimentally observed anomalies originate from these discrete energy states. For the better illustration of our point of view the reader is asked to look into recent Phys.Rev.Lett. papers. In Ref. 15 authors, considering states of two 3d electrons of the V3+ ion in V2O3, came out with the continuum electronic structure spread over 2.5 eV (Figs 2 and 3). In Ref. 16 the continuum electronic structure for six 3d electrons in FeO spreads over 8 eV (Fig. 8). In Refs 15-17 the orbital moment and the spin-orbit coupling is completely ignored. By this Letter we put the conjecture that in these cases the d electrons form the crystal-field discrete energy states with the importance of the s-o coupling. In FeO, in the paramagnetic state, a quite similar structure to that presented in Refs 4 and 6 is realized. We are convinced that the publishing of our paper enables the open scientific discussion on the magnetism and the electronic structure of 3d/4f/5f-atom containing compounds and we are ready for this discussion.


text:
# Feasibility of biepitaxial YBa2Cu3O7-x Josephson junctions for fundamental studies and potential circuit implementation

## I Introduction

The possibility of realizing electronic circuits in which the phase differences of selected Josephson junctions are biased by $`\pi `$ in equilibrium is quite stimulating.  The concept of such $`\pi `$-phase shifts was originally developed in the “extrinsic” case for junctions with ferromagnetic barriers  and in the “intrinsic” case for junctions exploiting superconductors with unconventional order parameter symmetries.  As a result of the possible d$`_{x^2y^2}`$ order parameter symmetry of high critical temperature superconductors (HTS),  the presence of intrinsic $`\pi `$ loops has also been considered for HTS systems.  This has been discussed recently in view of novel device concepts, and in particular for the implementation of a solid state qubit  and for Complementary Josephson junction electronics.  In this paper we discuss how YBa2Cu3O7-x (YBCO) structures made by the biepitaxial technique  can be successfully employed to produce arbitrary circuit geometries in which both “0” and $`\pi `$-loops are present, and possibly to obtain a doubly degenerate state.  Of course, great caution should be used because of stringent requirements on junctions parameters for practical applications of such devices.

Josephson junctions based on artificially controlled grain boundaries have been widely employed for fundamental studies on the nature of HTS.  The lack of a reliable technology based on the traditional trilayer configuration (i.e. a sandwich type junction with an insulator between the two superconducting electrodes) also enhanced interest in GB Josephson junctions for applications. Although the mechanism of high-TC superconductivity and the influence of grain boundaries on the transport properties are not completely determined, reproducible and good quality devices are routinely fabricated. YBCO GB junctions are usually classified as bicrystals,  biepitaxials,  and step-edges,  depending on the fabrication procedure. The bicrystal technique typically offers junctions with better performances and allows in principle the realization of all different types of GBs ranging from  and  tilt to  twist boundaries. GB junctions based on the step-edge and biepitaxial techniques offer the advantage, with respect to the bicrystal technology, of placing the junctions on the substrate without imposing any restrictions on the geometry. A comparison between the different GB techniques is far beyond the aim of this paper. Nevertheless we intend to show that significant improvements with respect to the original technique developed by Char et al.  are possible for biepitaxial junctions, and that the resulting devices have potential for applications. As a matter of fact, in traditional biepitaxial junctions, the seed layer used to modify the YBCO crystal orientation on part of the substrate produces an artificial 45  tilt (c-axis tilt) GB. The nature of such a GB seems to be an intrinsic limit for some real applications. A convincing explanation has been given in terms of the d-wave nature of the order parameter and more specifically by the presence of $`\pi `$-loops.  As demonstrated by studies on bicrystals, based on the same type of 45  tilt GB, the presence of $`\pi `$ -loops reduces the ICRN values (where IC and RN are the critical current and the high normal state resistance respectively), produces a dependence of the critical current IC on the magnetic field H quite different from the Fraunhofer-like pattern, and generates unquantized flux noise at the grain boundary.

We will show that the implementation of the biepitaxial technique  we developed to obtain 45  tilt and twist (a-axis tilt and twist) GBs junctions makes such a technique interesting for both applications and fundamental studies. The phenomenology observed for the junctions based on these GBs and Scanning SQUID Microscopy investigations demonstrate the absence of $`\pi `$-loops, as we expect from their microstructure. As a consequence higher values of the ICRN values, a Fraunhofer like dependence of IC on the magnetic field and lower values of the low frequency flux noise, when compared with 45 c-axis tilt GBs, have been measured. These features are important tests to employ junctions for applications. Scanning SQUID Microscopy investigations also gave evidence of “fractional” vortices in the presence of impurities. Finally, we extended the biepitaxial process to other types of GB by using different seed layers to obtain junction configurations where $`\pi `$ loops can be controllably produced. We shall not dwell on conceptual principles and actual feasibility of qubit devices. Instead we discuss the importance of the biepitaxial technique in having “0” and “$`\pi `$” loops on the same chip. This makes the biepitaxial technique more versatile and promising for circuit design.

## II Devices: concepts and fabrication procedure

As mentioned above, the biepitaxial technique allows the fabrication of various GBs by growing different seed layers and using substrates with different orientations. We have used MgO, CeO2 and SrTiO3 as seed layers. The MgO and CeO2 layers are deposited on (110) SrTiO3 substrates, while SrTiO3 layers are deposited on (110) MgO substrates; in all these cases the seed layers grow along the  direction. Ion milling is used to define the required geometry of the seed layer and of the YBCO thin film respectively, by means of photoresist masks. YBCO films, typically 120nm in thickness, are deposited by inverted cylindrical magnetron sputtering at a temperature of 780 C. YBCO grows along the  direction on MgO (substrates or seed layers) and on the CeO2 (seed layers), while it grows along the / direction on SrTiO3 (substrates or seed layers). In order to select the  or \[$`\overline{1}`$03\] growth and to ensure a better structural uniformity of the GB interface, we have also successfully employed vicinal substrates. However, most of the transport properties presented in this paper refer to samples not using vicinal substrates. Detailed structural investigations on these GBs, including Transmission Electron Microscopy (TEM) analyses, have been performed and the results have been presented elsewhere.

Depending on the patterning of the seed layer and the YBCO thin film, different types of GBs ranging from the two ideal limiting cases of 45 a-axis tilt and 45 a-axis twist have been obtained (see Fig.1). The intermediate situation occurs when the junction interface is tilted at an angle $`\alpha `$ different from 0 or $`\pi `$/2 with respect to the a- or b-axis of the  YBCO thin film. In all cases, the order parameter orientations do not produce an additional $`\pi `$ phase shift along our junction, in contrast with the 45 asymmetric  tilt junctions. As a consequence, no $`\pi `$ loops should occur independently of the details of the interface orientation. In Fig. 1 we consider ideal interfaces and neglect meandering of the GBs or interface anomalies that will be considered below. The CeO2 seed layer may produce a more complicated GB structure, in which a 45 c-axis tilt accompanies the 45 a-axis tilt or twist (see Fig.2a).  In this case, as shown in Fig.2b, $`\pi `$ loops should occur in analogy with the traditional biepitaxial junctions based on 45 c-axis tilt GBs. In both Figs. 1 and 2 we display the possible d$`_{x^2y^2}`$ -wave order parameter symmetry in the junction configuration. Junctions were typically 4 microns wide. We also performed systematic measurements on SQUIDs based on the structure employing MgO as a seed layer and SrTiO3 as a substrate. DC SQUIDs in different configurations and with loop inductance typically ranging from 10 to 100 pH have been investigated. The typical loop size leading to the 10(100) pH inductance is approximately 102$`\mu `$m2 (104$`\mu `$m2).

## III Experimental results

### A Biepitaxial junctions employing MgO seed layers

In this section we attempt to cover most of the phenomenology of the transport properties of 45 a-axis tilt and twist biepitaxial junctions. In Fig. 3, current vs voltage (I-V) characteristics of a typical biepitaxial junction are given for various temperatures close to the critical temperature. In the inset the corresponding I-V characteristic at T = 4.2 K is reported. They are closely described by the resistively-shunted-junction (RSJ) model and no excess current is observed. Nominal critical current densities JC of 5 x 102A/cm2 at T = 77 K, and of 9 x 10 3A/cm2 at T = 4.2 K have been measured respectively. The RN value (3.2 $`\mathrm{\Omega }`$) is roughly independent of the temperature for $`T<T_C`$, providing a normal state specific conductance $`\sigma _N`$ = 70 ($`\mu `$$`\mathrm{\Omega }`$cm2)-1. The maximum working temperature TC of this device was 82 K. In this case ICRN is 1.3 mV at T = 4.2 K. These values typically ranged from 1 mV to 2 mV at T = 4.2 K. They are larger for the corresponding JC values than those provided by conventional biepitaxials, and are of the same order of magnitude as in GB bicrystal and step edge junctions.  While the values of critical current density and normal state specific conductance in the tilt case are quite different from the twist case, the ICRN values are approximately the same for both. Moreover ICRN does not scale with the critical current density.  In the tilt cases JC $``$ 0.5-10 103 A/cm2 and $`\sigma `$N $``$ 1-10 ($`\mu `$$`\mathrm{\Omega }`$cm2)-1 are measured at T = 4.2 K respectively. Twist GBs junctions are typically characterized by higher values of JC in the range 0.1-4.0 x 105 A/cm2 and of $`\sigma `$N in the range 20-120 ($`\mu `$$`\mathrm{\Omega }`$cm2)-1 (at T = 4.2 K). For the twist case deviations from the RSJ model are more marked as a result of higher critical current densities. For high values of JC GB junctions do not present any clear modulation of the critical current as a function of the magnetic field.

A demonstration of the possibility of tailoring the critical current density and of the different transport regimes occurring in the tilt and twist cases has been given by measuring the properties of junctions with different orientations of the GB barrier on the same chip. By patterning the seed layer as shown in Fig.4a, we could measure the properties of a tilt junction and of junctions whose interface is tilted in plane by an angle $`\alpha `$ = 30, 45 and 60 with respect to the a- or b-axis of the  YBCO thin film respectively. In all cases the order parameter orientations do not produce an additional $`\pi `$ phase shift along our junction, in contrast with the 45  tilt junctions, and no $`\pi `$ loops should occur. We measured the expected increase of the critical current density with increasing angle, which corresponds on average to an increase of the twist current component. The values measured at T = 4.2 K are reported in Fig. 4a and range from the minimum value JC = 3 x 102 A/cm2 in the tilt case to the maximum JC = 104 A/cm2 corresponding to an angle of 60, for which the twist component is higher. The consistency of this result has been confirmed by the values of normal state resistances, which are higher in the tilt case and decrease with increasing $`\alpha `$. The ICRN values are about the same for all the junctions independently of the angle $`\alpha `$. In Fig. 4b the I-V characteristics measured at T = 4.2 K, corresponding to the junctions of Fig.4a, are shown for approximately the same voltage range. Deviations from RSJ behavior appear for higher values of the critical current density ($`\alpha `$ = 60). These results demonstrate that the grain boundary acts as a tunable barrier. This possibility of modifying the GB macroscopic interface plane by controlling the orientation of the seed layer’s edge is somehow equivalent to the degree of freedom offered by bicrystal technology to create symmetric or asymmetric GBs, with the advantage of placing all the junctions on the same substrate. The 45 a-axis tilt and twist GBs and the intermediate situations can represent ideal structures to investigate the junction physics in a wide range of configurations. The anisotropy of the (103) films and the possibility to select the orientation of the junction interface by suitably patterning the seed layer, and eventually the use of other seed layers which produce different YBCO in plane orientations, allow the fabrication of different types of junctions and the investigation of different aspects of HTS junction phenomenology. In particular we refer to the possibility of changing the tunneling matrix elements (by selecting the angle $`\alpha `$) and to use the anisotropy of the layered structure of YBCO properties and of the order parameter symmetry.

The study of the junction properties in the presence of an external magnetic field H is a fundamental tool for the investigation of the Josephson effect in the various junctions, as well as a test of junction quality.  We observe modulations of the critical current IC following the usual Fraunhofer-like dependence. The IC (H) patterns are mostly symmetric around zero magnetic field, and in all samples the absolute maximum of IC occurs at H=0. The presence of the current maximum at zero magnetic field is consistent with the fact that in our junction configuration the order parameter orientations do not produce an additional $`\pi `$ phase shift, in contrast with the 45  tilt GB junctions.  Some examples are given in Fig. 5, where the magnetic pattern relative to a SQUID and a single junction at T = 4.2 K are shown respectively. In the former case we can also distinguish a smaller field modulation (with a period of 8 mG) which corresponds to the SQUID modulation (inset a). In the latter case the I-V characteristics are reported for different magnetic fields (inset b). Despite the Fraunhofer-like dependence, some deviations are evident, in agreement with most of the data available in literature.

For sake of completeness we also acknowledge some work we carried out by investigating Fiske steps as a function of H in other junctions, giving some evidence of a dielectric-like behavior  of some of the layers at the junction interface. We already reported about this work elsewhere.  The Fiske steps do not depend on the use of a particular substrate, since they have been observed in junctions based both on SrTiO3 and MgO substrates. Typical values of the ratio between the barrier thickness t and the relative dielectric constant $`ϵ_r`$ range from 0.2 nm to 0.7 nm. Considerations on the dependence of IC on the temperature (T) can be also found in Ref.. In junctions characterized by lower critical current densities, IC tends to saturate at low temperatures, in contrast to those characterized by higher critical currents, for which there is a linear increase.

### B Scanning SQUID microscopy on biepitaxial junctions with MgO seed layer

Figure 6 is a scanning SQUID microscope image of a 200x200$`\mu `$m2 area along a grain boundary separating a (100) region from a (103) region (as labelled in the figure) of a thin YBCO biepitaxial film grown as described above. The position of the grain boundary is indicated by the dashed line. The image was taken at 4.2K in liquid helium with an octagonal SQUID pickup loop 4 microns in diameter after cooling the sample in a few tenths of a $`\mu `$T externally applied magnetic field normal to the plane of the sample. The grey-scaling in the image corresponds to a total variation of 0.13$`\mathrm{\Phi }_0`$ of flux through the SQUID pickup loop. Visible in this image are elongated interlayer Josephson vortices in the (103) area to the right, and “fractional” vortices in the (100) area to the left, of the grain boundary. Fits to the interlayer vortices give a value for the $`c`$-axis penetration depth of about 4$`\mu `$m. The “fractional” vortices are spontaneously generated in the (100) film, regardless of the value of external field applied. Temperature dependent scanning SQUID microscope imaging shows that this spontaneous magnetization, which appears to be associated with defects in the film, arises when the film becomes superconducting. Although it is difficult to assign precise values of total flux to the “fractional” vortices, since they are not well separated from each other, fits imply that they have less than $`\mathrm{\Phi }_0`$ of total flux in them, an indication of broken time-reversal symmetry. Although there is apparently some flux generated in the grain boundary region, the fact that these SQUIDs have relatively low noise seems to indicate that this flux is well pinned at the temperatures at which the noise measurements were made. These results are consistent with the absence of $`\pi `$ loops along the grain boundary.

### C  Biepitaxial junctions employing CeO2 seed layers

The CeO2 seed layer, as anticipated in section II, may produce an artificial GB that can be seen as a result of two rotations: a 45  tilt or twist followed by a 45  tilt around the c-axis of the (001) film. For this junction configuration a d-wave order parameter symmetry would produce $`\pi `$-loops, as shown in Fig. 2. We notice that such $`\pi `$-loops are structurally different from those usually obtained by the 45  tilt GB junctions based on the traditional biepitaxial and bicrystal techniques. Due to the microstructure we expect especially in the  tilt case low critical current densities and high normal state resistances. We found that the deposition conditions to select the uniform growth of YBCO 45 tilted around the c-axis of the (001) film are critical. Preliminary measurements realized on tilt-type junctions with a CeO2 seed layer gave evidence of Josephson coupling in these GBs. The measured ICRN values are from 200 $`\mu `$V to 750 $`\mu `$V and are in the typical range of the GBs Josephson junctions.

### D Biepitaxial SQUIDs employing MgO seed layers

In this section we report on the characterization of dc-SQUIDs which are to our knowledge the first employing the GBs discussed above.  These SQUIDs exhibit very good properties, and noise levels which are among the lowest ever reported for biepitaxial junctions.  Apart from implications for applications, these performances are important for the study of the transport properties of HTS Josephson junctions. In Fig. 7 we show the magnetic field dependence of the voltage at 77 K for different values of the bias current for a dc-SQUID with an inductance of 13 pH. At this temperature ICRN is about 20 $`\mu `$V. The corresponding value of the screening parameter $`\beta `$=2LIC/$`\mathrm{\Phi }_O`$ is 0.03. In general low $`\beta `$ values are mandatory to avoid the influence of asymmetric inductances in SQUID properties, and this has been crucial for experiments designed to study the order parameter symmetry. The presented curves are quite typical. These SQUIDs usually work in a wide temperature range from low temperatures (4.2 K ) up to temperatures above 77 K. The maximum working temperature was in this case 82 K. The achieved magnetic flux-to-voltage transfer functions VΦ = $``$V/$`\mathrm{\Phi }`$, where V and $`\mathrm{\Phi }`$ are the voltage across the device and the applied magnetic flux in the SQUID loop respectively, are suitable for applications. For instance at T = 77 K an experimental value of the SQUID amplitude voltage modulation $`\mathrm{\Delta }`$V of 10.4 mV was measured, corresponding to VΦ = 36.9 $`\mu `$V/$`\mathrm{\Phi }_0`$.  Steps of different nature have been recurrently observed in the I-V characteristics in the washer and hole configurations and characterized also in terms of the magnetic field dependence of the voltage at different values of the bias current.

The noise spectral densities of the same dc-SQUID have been measured at T = 4.2 K and T = 77 K using standard flux-locked-loop modulated electronics. The energy resolution $`ϵ`$ = SΦ/2L (with SΦ being the magnetic-flux-noise spectral density) at T = 4.2 K and T = 77 K is reported in Fig. 8. At T = 4.2 K and 10 kHz, a value of SΦ = 3 $`\mu \mathrm{\Phi }_0`$/$`\sqrt{Hz}`$ has been measured, corresponding to an energy resolution $`ϵ`$ = 1.6x10-30 J/Hz. This value is the lowest reported in the literature for YBCO biepitaxial SQUIDs. Moreover, the low frequency 1/f flux noise spectral density at 1 Hz is more than one order of magnitude lower than the one reported for traditional biepitaxials, as is also evident from the comparison with data at T = 4.2 K of Ref. . The lower values of low frequency noise are consistent with the absence of $`\pi `$-loops on the scale of the faceting for these types of GBs, as clearly shown by Scanning SQUID Microscopy results. The $`\pi `$-loops produce some types of spontaneous magnetic flux in the GB region, which among other effects tends to degrade the SQUID’s noise levels.

## IV Biepitaxial junctions for experiments on the symmetry of the order parameter and for a development of concepts for qubits

The particular junction configurations investigated in this work allow some consideration of the possible impact of these types of junctions on the study of the Josephson effect and the order parameter symmetry in YBCO and on the development of concepts for devices.  We first recall that the biepitaxial technique can provide circuits composed completely of junctions without any $`\pi `$-loops (see Fig. 9a). By varying the interface orientation with respect to the  electrode orientation, the junction properties can be adjusted. On the other hand the traditional biepitaxial technique,  producing 45  tilt GBs (see Fig. 9b) or the types of junctions described in the previous section by using CeO2 (see Fig. 9c), can controllably generate $`\pi `$-loops on macroscopic scales. In these schemes we use a corner geometry with a 90 angle. This angle $`\alpha `$ can be obviously tuned to enhance the effects related to the phase shift (see dashed line in Fig.9b) and this change is particularly easy to realize by using the biepitaxial technique.

In this section we focus our attention mainly on the feasibility of the biepitaxial junctions to obtain the doubly degenerate state required for a qubit. In Ref.a the design is based on quenching the lowest order coupling by arranging a junction with its normal aligned with the node of the d-wave order parameter, thus producing a double periodic current-phase relation. It has been shown that the use of $`\pi `$ phase shifts in a superconducting phase qubit provides a naturally bistable device and does not require external bias currents and magnetic fields. b The direct consequence is the quietness of the device over other designs. A $`\pi `$ junction provides the required doubly degenerate fundamental state, which also manifests itself in a doubly periodic function of the critical current density as a function of the phase.  The same principle has been used in small inductance five junction loop frustrated by a $`\pi `$-phase shift. b This design provides a perfectly degenerate two-level system and offers some advantages in terms of fabrication ease and performance. HTS may represent a natural solution for the realization of the required $`\pi `$-phase shift due to the pairing symmetry of the order parameter and, therefore, due to the possibility of producing $`\pi `$ phase shifts. Experimental evidence of YBCO $`\pi `$ -SQUIDs has been given by employing the bicrystal technique on special tetracrystal substrates.  The biepitaxial technique, beyond providing junctions with opportune properties, would guarantee the versatility necessary for the implementation of a real device, as shown below. As a matter of fact, we notice that our technique allows the realization of circuits where $`\pi `$-loops can be controllably located in part of the substrate and separated from the rest of the circuit based on “0”-loops, i.e. junctions where no additional $`\pi `$ phase shifts arise. This can be easily made by depositing the MgO and CeO2 seed layers on different parts of the substrate, which will be also partly not covered by any seed layer.

As a test to show how the biepitaxial junctions could be considered for preliminary tests and device implementation for quantum computing without the topological restriction imposed by the bicrystal technique, we refer to the structures proposed in Ref.as exemplary circuits.

The former is composed by a s-wave (S)- d-wave (D)- s-wave (S’) double junction connected with a capacitor and an ordinary “0” Josephson junction based on s-wave superconductors (the S-D’-S junction generates the doubly degenerate state). The latter consists of a five junction loop with a $`\pi `$ junction. Our technique would combine the possibility of placing the ordinary “0” junctions corresponding to the MgO seed layer and to exploit the possible doubly degenerate state of asymmetric 45 GB junctions corresponding to the CeO2 seed layer to replace the S-D-S’ system or the $`\pi `$ junction respectively. Our structure would be obviously composed only of HTS. In Figs. 10a and 10b we show how devices for instance such as those proposed in Ref. could be obtained by employing the biepitaxial technique respectively. The application to the five junction loop is straightforward (Fig.10b) and the advantages of this structure have been already discussed in Ref. b. The biepitaxial technique can offer possible alternatives for the realization of the structures above. In particular the double junctions of the original S-D-S’ system can be also replaced by a D’-D-D” structure (Fig.10c) by exploiting our technique, in contrast to the bicrystal technology which could not give this possibility. Such a configuration could offer some advantages, if we consider that asymmetric 45 bicrystal GB Josephson junctions did not give systematic evidence of the doubly degenerate state. The doubly degenerate state seems to occur only in high quality low transparency GB junctions  and it is known that S-I-D junctions do not have double periodicity of the critical current as a function of the phase.  A consequence of a possible nodeless order parameter  at the D-D’ GB interface could be a closer similarity with a S-I-D junction with loss of the doubly degenerate state. If this is the case, we speculate that the double junctions structure for symmetry reasons would produce a leading term in the Josephson coupling energy of the form Ed cos2$`\theta `$ (double periodic) and that the possible dipolar component of the magnetic field would be almost completely compensated in this configuration. b This can be considered as an attempt to construct a “microscopic” 2$`\theta `$-junction. We finally notice that the topological advantages offered by the biepitaxial junctions would therefore be crucial in both the cases considered for the realization of the structure in Fig. 10, and important to reduce de-coherence effects. Bicrystal substrates would in fact impose on the circuit additional junctions required by the circuit design and, as a consequence, generate additional noise and de-coherence in the device.

## V Conclusions

The performance of the presented junctions and SQUIDs demonstrates that significant improvements in the biepitaxial technique are possible, and the resulting devices have potential for applications. We have presented a phenomenology that is consistent with the expected absence of $`\pi `$-loops in 45  tilt and twist grain boundaries junctions. The use of a CeO2 rather than a MgO seed layer can produce $`\pi `$-loops in the same junction configurations. The versatility of the biepitaxial technique has been recently used to obtain different types of grain boundaries. The advantage of placing junctions in arbitrary locations on the substrate without imposing any restrictions on the geometry, and the ease of obtaining different device configurations by suitably patterning the seed layer, make the biepitaxial technique competitive for the testing of new concept devices, such as those based on $`\pi `$-loops. Some simple examples of situations in which $`\pi `$-loops can be suitably produced in specific locations of a more complicated circuit have also been discussed.

###### Acknowledgements.

This work has been partially supported by the projects PRA-INFM “HTS Devices” and SUD-INFM “Analisi non distruttive con correnti parassite tramite dispositivi superconduttori” and by a MURST COFIN98 program (Italy). The authors would like to thank Dr. E. Ilichev and A. Golubov for interesting discussions on the topic.