# Magnetic reconstruction at (001) CaMnO3 surface

## Abstract

The Mn-terminated (001) surface of the stable anti-ferromagnetic insulating phase of cubic perovskite CaMnO<sub>3</sub> is found to undergo a magnetic reconstruction consisting on a spin-flip process at surface: each Mn spin at the surface flips to pair with that of Mn in the subsurface layer. In spite of very little Mn-O charge transfer at surface, the surface behavior is driven by the $`e_g`$ states due to $`d_{xy}`$ $``$ $`d_{z^2}`$ charge redistribution. These results, based on local spin density theory, give a double exchange like coupling that is driven by $`e_g`$ character, not additional charge, and may have relevance to CMR materials.

Despite the abundance of work on manganese-based perovskites in the attempt to understand the rich panorama of their bulk properties, very little is known about their surfaces or interfaces. The physical mechanism inducing the so-called colossal magnetoresistance (CMR) in La<sub>1-x</sub>D<sub>x</sub>MnO<sub>3</sub> (with D a divalent alkaline earth ion, and $`x0.3`$) is yet to be fully understood, although it seems clear that the almost half-metallic nature (i.e. the complete spin-polarization of the electrons at the Fermi level) plays a decisive role. The clearest evidence so far of half-metallicity is from photoemission spectra, whose surface sensitivity makes it essential to know the electronic structure of the surface itself. The surface introduces the likelihood of square pyramidal coordinated Mn, which is also essential to the understanding of oxygen-deficient perovskite manganites. In addition, the interfacial behavior that is critical in producing low field CMR in polycrystalline material and trilayer junctions will involve closely related effects due to symmetry lowering of the Mn ion. Thus, studies of the surfaces of manganites are timely.

The electronic structure of the stable phase of bulk CaMnO<sub>3</sub> has been actively investigated in recent years. CaMnO<sub>3</sub> is a G-type antiferromagnetic (AFM) semiconductor. The nominal ionic picture Ca<sup>2+</sup>Mn<sup>4+</sup>O$`{}_{3}{}^{}{}_{}{}^{2}`$ with spherical Mn d<sup>3</sup> configuration, makes the cubic (fcc) phase stable over possible distortions observed for instance in LaMnO<sub>3</sub>. In the G-type arrangement all nearest neighbors in the simple-cubic sublattice of Mn have spin-antiparallel orientation. The chemical picture of Mn<sup>4+</sup> ions is represented by completely occupied d t$`{}_{}{}^{}{}_{2g}{}^{}`$ states. An energy gap of $``$ 0.4 eV separate them from the empty d e$`{}_{}{}^{}{}_{g}{}^{}`$ orbitals. Hybridization with O p states reduces the 3 $`\mu _B`$ nominal magnetization of Mn to $``$ 2.5 $`\mu _B`$, whereas magnetic moments on O or Ca are zero by symmetry.

In this paper we study the simplest manganite surface, the (001) surface of cubic CaMnO<sub>3</sub>, to determine the surface-induced changes of structural, electronic, and magnetic properties. We find unexpectedly rich effects of surface symmetry lowering: a spin-flip occurs on the surface Mn ions that can be traced to surface states that redistribute charge and spin amongst the various Mn $`d`$ suborbitals and render it metallic without doping. The net effect is a short-range double-exchange-like phenomenon that relates metallicity and spin alignment, analogous to the CMR phases.

Calculations were done in a local-spin-density framework; the exchange-correlation potential formula by Perdew and Zunger was used. A plane-wave basis with 30 Ryd cut-off energy and Vanderbilt pseudopotentials make the computation viable. To establish the accuracy of our methods, which have only recently been applied to magnetic materials, in Table I we report our results for the bulk CaMnO<sub>3</sub> in different magnetic phases. As already shown, for manganese perovskites the local spin density approximation successfully predicts the observed stable phase not only against the strongly unfavoured paramagnetic (PM) phase, but also in competition with closer configurations like the ferromagnetic (FM) and the A-type AFM (made of (001) FM layers alternating along  direction). Our results are in very good agreement with those of previous all-electron linear-augmented plane-wave calculations. Also, our calculated value for the equilibrium lattice constant of G-type AFM phase (3.735 Å) is in almost perfect agreement with the experimental value (3.729 Å).

The stacking along  consists of alternating MnO<sub>2</sub> and CaO units (see Fig. 1), and the surface unit cell of G-type AFM CaMnO<sub>3</sub> is $`\sqrt{2}\times \sqrt{2}`$ with respect to that of the bulk cubic cell (we neglect the very small structural distortion). The (001) layers are individually AFM and neutral, so the surface is formally non-polar. Surface formation produces two different surfaces, i.e. Mn-terminated and Ca-terminated. The presence of two inequivalent surfaces in a slab will produce fictitious fields in the vacuum that could affect the electronic and magnetic structure at the surface. We are interested on the Mn-terminated surface, since on it the effects on magnetic properties due to the surface formation are most visible. Thus we use a slab containing two identical Mn-terminated surfaces, with mirror symmetry in the central Mn layer (in total a 46-atom slab with 9 layers of atoms and 3 of vacuum).

Surface neutrality generally favours the stability of the ideal surface against reconstructions involving strong changes of symmetry and atomic density at surface. Therefore in this work we consider the surface with relaxed but structurally unreconstructed structure, with different types of magnetic order. Thus we will speak of ‘reconstruction’ in purely magnetic sense: on the unreconstructed surface the spins are oriented as in the bulk (Figure 1), while the reconstructions involve spin-flips on the surface layer.

The structure of the two configurations that can be obtained by flipping surface spins are pictured in Fig. 2. In the left panel all surface spins are flipped, so vectors $`(\pm a,\pm a)`$ remain AFM translations but each surface spin is aligned with its subsurface neighbor (spin-flip AFM: sf-AFM). In the right panel only one (of two) surface spins is flipped, leaving a FM surface layer (spin-flip FM: sf-FM).

Magnetic and relaxation energies and workfunctions for the three phases are reported in Table II. The $`\mathrm{\Delta }E`$’s reported in Table II are the energies gained by relaxing all the atoms into the slab from their ideal positions. They are small and reflect the small inward atomic displacements $``$ 1% of the cubic lattice constant. This indicates a low excess stress due to the surface formation, and suggests that structural reconstructions are unlikely. The workfunction depends very little on the spin arrangement but is largest for the most stable surface. Most significantly, the sf-AFM surface is stable against the unreconstructed one, whereas the sf-FM is the most unfavoured. Thus, a quite intriguing physical picture follows: at the surface each spin prefers to pair with the one in the subsurface layer, while still keeping the AFM arrangement in-plane. 

It is possible to express the energy differences for differing types of magnetic order in terms of exchange constants in a Heisenberg model

$$H=\underset{<ij>}{}J_{ij}\widehat{S}_i\widehat{S}_j$$
(1)   
where $`\widehat{S}_j`$ is a unit vector in the direction of the moment on site $`j`$, and the sum is over distinct pairs. For the bulk we get first and second neighbor constants $`J_1=26`$ meV, $`J_2=4`$ meV. This small value of $`J_2`$ suggest that the nearest neighbor (nn) exchange constants contain the important contributions. From surface energies we get the nn coupling parallel and normal to the surface of $`J^{}`$= -22 meV, $`J^{}`$ = 29 meV. While $`J^{}`$ is close to the bulk value, $`J^{}`$ has the opposite sign and is larger in magnitude, indicating the FM alignment of surface and subsurface spins is robust.

The reversal of the surface-subsurface coupling can be traced to redistribution of $`d`$ suborbital occupations compared to the bulk, due to the occurrence of surface states. The orbital-projected Mn 4$`d`$ density of states (DOS) of the stable sf-AFM phase near the Fermi level, shown in Fig. 3, makes evident the surface states that lie within the bulk band gap, which extends from -0.3 eV to 0.1 eV relative to E<sub>F</sub>. The surface states are of two distinct types, $`d_{z^2}`$ and $`d_{xy}`$, reflecting the strong symmetry lowering of both $`e_gd_{z^2},d_{x^2y^2}`$ and $`t_{2g}d_{xy},(d_{xz},d_{yz})`$ manifolds. The surface states are almost completely polarized, a result of the large spin splitting $`\mathrm{\Delta }_{ex}`$ =2 eV that strongly inhibits hopping between ions of different spin.

Figure 4 presents the surface band structure, where for clarity, only the energy region of interest (roughly spanning the bulk gap) is shown. The $`d_{xy}`$ and $`d_{z^2}`$ surface states are easily identifiable. The $`d_{xy}`$ states at the surface are shifted upward by 1 eV and overlap with $`d_{z^2}`$ states that in the bulk hybridize strongly with the O $`p\sigma `$ orbitals and form low-lying bonding and high-lying antibonding bands (most of the d weight is in the latter). The two $`d_{z^2}`$ states (one from each surface of the slab) are split by 0.2 eV as a result of the interaction between Mn at opposite sides of the slab. (For a thicker slab they would converge to a single, doubly degenerate band, averaging the calculated $`d_{z^2}`$ states). The $`d_{xy}`$ band has a bandwidth of 1.4 eV and a dispersion that follows

$$\epsilon _k^{xy}=2t[cos(k_x+k_y)a+cos(k_xk_y)a]$$
(2)   
using the conventional perovskite coordinates. This dispersion arises from hopping between second nn, which are the nearest neighbors of like spin. The effective hopping amplitude is $`t`$ = 0.17 eV. The $`d_{z^2}`$ band is very narrow (0.2 eV) and its dispersion is not easily represented by tight binding form, reflecting small competing hopping processes along the surface (and perhaps subsurface) that are not easily identified. Coupling of the $`d_{z^2}`$ state perpendicular to the surface is large, however, as reflected in the penetration of the state onto the fifth atomic layer (third Mn layer).

The net effect on the Mn ion of surface formation is an intra-atomic shift of charge from $`d_{xy}`$ to $`d_{z^2}`$ orbital, without appreciable change of charge or moment. In the solid the magnetic moment comes almost entirely from t<sub>2g</sub> states, whereas on the surface $`d_{z^2}`$ (surface) states contribute about 30% of the moment. Only the subsurface Mn in the sf-AFM phase experiences a net gain (0.07 $`\mu _B`$) due to the partially occupied $`d_{z^2}`$ state not compensated by a depletion of $`d_{xy}`$ states. In bulk, magnetic moments in the G-type bulk are only allowed on Mn, by symmetry. With the surface formation, O in-plane with Ca acquire a magnetic moment as well. This is larger in the sf-AFM (0.11 $`\mu _B`$) than in the unreconstructed phase (0.06 $`\mu _B`$), because it is enhanced by the parallel alignment of two neighboring Mn spins.

Most of the characteristics inferred by DOS and band structure analysis can be better visualized by means of isosurface plots (Fig. 5) of charge density and magnetization of the stable sf-AFM phase. The quantities shown are due only to states within the bulk gap (see Figure 4), thus represent charge and magnetization of the surface states. The charge density clearly shows both $`d_{xy}`$ and $`d_{z^2}`$ characters of the charge on Mn, as well as a $`p_\pi `$-type contribution from O.

The physical mechanism driving the changes in exchange interaction parameters at the surface is related to that described by Solovyev et al. investigating how the Jahn-Teller distortions (JTD) affect the magnetic ordering of LaMnO<sub>3</sub>. The basic driving force in the FM-to-AFM transition of LaMnO<sub>3</sub> vs. JTD is the decreasing of $`d_{z^2}`$ occupancy occurring with JTD. The $`d_{z^2}d_{z^2}`$ interaction is indeed a dominant positive (i.e. FM) contribution to $`J^{}`$. Also positive are the $`d_{x^2y^2}d_{z^2}`$ and the much weaker $`d_{x^2y^2}d_{x^2y^2}`$ interactions, whereas t<sub>2g</sub> orbitals interact by superexchange, and their contribution is AFM. When the $`d_{z^2}`$ orbitals are sufficiently occupied to make $`J^{}`$ larger than the next nearest neighbor interactions (favouring AFM) the order becomes FM along the $`\widehat{z}`$ axis.

In the present case the picture follows analogously: surface formation, not JTD, results in dehybridization and partial filling of the $`d_{z^2}`$ states on surface (and subsurface) Mn, and a partial depletion of $`d_{xy}`$ orbitals. As a consequence $`J^{}`$ changes sign and the magnetic ordering along $`\widehat{z}`$ reverses. A verification of this mechanism is given by comparison of the band structures (or DOS) of the two competing phases (Figure 4): in the sf-AFM phase there is more $`d_{z^2}`$ occupation and less $`d_{xy}`$ depletion than in the sf-FM phase. Also, the slight occupation of $`d_{z^2}`$ states on the subsurface atom is larger for the reconstructed sf-AFM phase, but not sufficient to propagate the spin alignment further into the bulk. The considerable difference with respect to the LaMnO<sub>3</sub> JTD is that its distortion is extended, whereas at the surface the ordering is a local effect limited to the first two layers. This local spin-flip process is likely to be relevant to more general situations in manganites, such as at surfaces and interfaces of doped systems where it may affect spin transport, and at Mn sites neighboring O vacancies, as in CaMnO<sub>3-x</sub>.

To summarize, we have described a spin-flip process at the Mn-terminated (001) surface of CaMnO<sub>3</sub> that is driven by symmetry lowering due to surface formation which causes the partial occupation of the $`e_g`$ $`d_{z^2}`$ surface states. This partially occupied narrow $`d_{z^2}`$ band may display correlated electron behavior. This $`d_{z^2}`$ occupation reverses the magnetic alignment (from AFM to FM) at the surface in the direction orthogonal to the surface but conserves the AFM symmetry along the surface. The surface states are almost completely polarized, but AFM symmetry requires that both spin states occur in equal number, so this result may be difficult to verify experimentally.

This research was supported by National Science Foundation grant DMR-9802076. Calculations were done at the Maui High Performance Computing Center.