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Solid State Communications,Vol. 98, No. 1,pp. 55-59,1996 Copyright @ 1996Published by Elsevier Science Ltd Printed in Great Britain. rights All resewed
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0038-1098(95)00786-S

ELECTRONIC

PHASE SEPARATION AND CHARGE ORDERING OF TRIPLET BIPOLARONS

IN (Sr,La)zMnOd: INDICATION

Wei Bao, * C. H. Chen, S. A. Carter and S-W. Cheong AT&T Bell Laboratories, Murray Hill, NJ 07974, U.S.A.
(Received 13 October 1995; accepted 10 November 1995 by A. Pinczuk)

Coexistence of two phases, having different in-plane dimensions, is found in the planar Srz_,La,MnOd for 0 < x I 0.38 at room temperature. Furthermore, charge ordering with modulation wave vector (7r/2, r-r/2) is discovered for x=0.5 below -250 K. Together with transport and magnetic measurements, these results indicate that the phase separation is due to the competition between the single and the double occupancies of the Mn 3d orbitals by the doped electrons. The doubly-occupying electrons form on-site triplets which are mobile at high temperatures and form a bipolaron lattice below -250 K. Keywords: A. magnetically ordered materials, D. exchange and superexchange, D. electron-phonon interactions, D. valence fluctuations, D. phase transitions

DISPROPORTIONATION of doped charge carriers in layered compounds has been of great interest in recent years. For example, La2Cu04+Y (0.01 5 y 5 0.07) exhibits macroscopic phase separation below Ts-260-320 K into an oxygen-rich superconducting phase and an oxygen-poor insulating antiferromagnetic (AF) phase with TN-T~ [l]. Theoretical studies of doped holes in the AF CuO2 plane have predicted hole segregation into hole-rich and hole-poor phases when the exchange energy J is larger than the hopping amplitude t [2]. An explanation is provided for La2Cu04+, as oxygen is mobile at Ts and can move with the holes to form the oxygen-rich and the oxygen-poor phases [3]. However, the origin of this phase separation is still controversial [4]. Microscopic disproportionations such as hole-pairs or the striped phase are also proposed [4,5]. The existence of a striped phase in Laz_$r,Cu04 (01x10.02) was infered from the finite size scaling of susceptibility [6]. In the isostructural Laz_,Sr,NiO4, doped holes are polaronic [7] and two-dimensional (2D) ordering of these polarons in diagonal stripes has been discovered for x=1/3 and l/2 below 235 K and 340 K respectively [8]. The 2D incommensurate short-range magnetic order below 100 K in Lar.sSro.2NiO4 [9] can be understood as a subsequent AF ordering within the * Permanent address: The Johns Hopkins University, Baltimore, MD 21218, U.S.A.

x=1 /3-type polaron-ordered domains. Here we report the discovery of a new kind of charge ordering, diagonal bipoluron stripes, below 250K in the isostructural Srz_,La,MnOa near x=1/2. Furthermore, we found strong evidence for macroscopic electronic phase separation in the doping range O<x10.38. Polycrystalline samples of Srs_,La,MnOa with O<x10.8 were synthesized by solid-state reaction. The starting materials LazOs, SrCOs and Mn02 were mixed in appropriate stoichiometric proportions and heated in air at 1300 C for 5 hours, 1400 C for 12 hours and 1480 C for 20 hours, with intermediate grindings. The magnetization was measured with a Quantum Design SQUID magnetometer, the resistivity p with the standard four-probe method and electron diffractions with a JEOL 2000FX transmission electron microscope. Powder X-ray diffraction patterns obtained with a Rigaku Minitlex diffractometer can be indexed in the tetragonal I4/mmm space group. Peaks within the range of 15<20<70 were used to obtain the lattice parameters a and c (Fig.l(a)). For 0.02<x<O.38, two sets of peaks corresponding to different basal dimension a appear. As shown in Fig.l(b), with increasing x, the (200) peak at smaller 28 angle (larger a) becomes stronger and sharper while the (200) peak at larger 28 (smaller a) becomes weaker and broader and eventually disappears at x=0.38(2). This indicates that the phase with larger a

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Sr,_,La,MnO, 0.10 x? ij E > 0.05 E al V

Sr,_,La,MnO,

12.5
0 0.5
X

1 54

w
0.4 0.5

0.00

57

5
; 0.3 Y 0.2 s; 0.1 0
0 100

28

Fig. 1. (a) Variation of lattice parameters in Srz_,La,MnOd at 300K. Squares are for c and closed circles a. Two phases with different Q exist for 0 < x zz 0.38. Diamonds are from Ref. [12], triangles Ref. [13]. (b) Evolution of (200) peaks with x in X-ray pattern (Co Ka) for representative samples. For clarity, the broad peaks are indicated by arrows. grows at the expense of the phase with smaller a. In order to probe the cause of these two phases, we tried various heat treatments for the x=0.2 samples, such as annealing in air at 1480 C for 100 hours, in 120 bar 02 at 650 C for 10 hours, quenching from 1480 C, 1150 C, 750 OC and 450 C in air. However, there is little change in the X-ray diffraction pattern. This indicates that the two different phases are not caused by oxygen diffusion or La and Sr segregation (unless the process is faster than quenching). Electron beam microanalysis with a -3OOAprobe did not detect any chemical separation of La and Sr ions. With the experimental results presented below, we shall argue for an electronic phase separation driven by the onsite exchange interaction. SrzMnOd is a 2D AF insulator. The Mn ion is tetravalent and has three 3d electrons. The susceptibility x, expanded 40 times in Fig.2(a), shows a broad peak, typical of a 2D antiferromagnet. Comparison with the results of high-temperature series expansion for S=3/2 [lo] yields an AF coupling constant J/k~=73(2) K. Earlier neutron diffraction showed that a 3D AF order of the K2NiF4-type sets in at T~=170 K [I 11, which is seen as a small anomaly in our x at -150 K. The staggered moment of 2.42pB/Mn at 4.2 K [l l] is slightly smaller than 3j.4~for three parallel spins. The three occupied de (or tzg) orbitals are separated from the two dy (or eg) orbitals by the crystal field splitting in an oxygen octahedron environment [14]. The conduction is thermally activated, as evidenced by the constant d lnp/dT- over the

200 T 6)

300

Fig. 2. Representative temperature dependences of (a) magnetization, measured with H=2T; and (b) Inversetemperature derivative of logarithmic resistivity, which corresponds to the thermal activation energy when flat. Curves are labeled by the La content x. Inset in (b), msistivity at 300 K vs. La content. entire measured temperature range in Fig.2(b). When electrons are introduced via substituting La3+ for Sr2+, the paramagnetic x above 250 K increases steadily before saturating at x - 0.5 (Fig.2(a)). A plot of x at 300 K vs. La content shown in Fig.3(a) better illustrates this trend. Earlier high temperature measurements for x=0.5 showed upward curvature in x-r(T) and a Curie-Weiss behavior above -600 K, yielding a positive 0=320 K and an effective moment of 4.18p&Mn [12]. This means that the doped electrons go into d, orbitals forming a high spin configuration and local ferromagnetic interaction is introduced. The diluted dy electrons form polarons by polarizing nearby ions and spins and facilitate the electric conduction. This is reflected in the sharp, 2-3 orders of magnitude, reduction of p at 300K with doping (inset of Fig.2(b)). However, the nonmetallic state remains stable over the entire doping range studied. This is similar to the 2D nickelate but contrary to the cuprate [8] and also contrary to the 3D manganate [I 51, for which there is renewed interest currently due to the large magnetoresistance [ 161 at the simultaneous ferromagnetic and insulator-to-metal transitions. At TM= 150 K, a ferromagnetic-like transition is ap-

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200K

T?-+=&2 ZOO- .d____TM

0
I

To
I /

e- 100-i
11
0.0

I,

Cd)
1.0

0.5 x in Sr,_,La,MnO,

Fig. 4. [OOl]zone-axis electron diffraction pattern obtained at 95 K for x=0.5. The sharp superlattice spots develop below TO - 250 K as a result of charge ordering with modulation (n/2, rr/2,0) or (7-r/2, a, 0). Right: the proposed (n/2,7-r/2,0) ordering pattern of triplet bipolarons (circles) with disordered spins on a Mn square lattice.

tal Bragg reflection and much weaker second order peaks are also present. No superlattice peaks can be Fig. 3. Composition dependence of (a) susceptibility x E dM/dH at 20 K (closed circles) and 300 K (open seen at room temperature and the appearance of them circles); (b) saturation moment at 20 K; (c) activation correlates well with the 250K transition. The two energy of transport at 200 K (closed circles) and at 300 different modulations, characterized by wave vectors K (open circles); and (d) characteristic temperatures: q=2n(6,6,0) and 2rr(6,& 0) in Fig.4, arise from closed circles, 3D magnetic ordering temperature TM two different types of domains rotated by 90 to each from magnetic measurement; squares, anomaly in x corresponding to the charge ordering TO;and triangle, other, as demonstrated by the selected area diffraction Neel temperature TN from Ref. [l 11. The dashed lines patterns in which only one type of modulation is observed. The superlattice modulation in Fig.4 is found delimit the two phase region. to be commensurate, &l/4. However, we note that parent in Fig.2(a) at high doping. In view of the small 6 varies slightly from one grain to another, typically saturation moment MO (refer to Fig.3(b)), this weak- from 0.23 to 0.25. The superlattice reflections with ferromagnetism could signal a 3D AF ordering, as 6=1/4, in general, are sharper than other values of 6, in the isostructural cuprates and nickelates [17]. TM suggesting a longer coherence length for this preferred is essentially composition independent as shown in commensurate modulation in the case of x=0.5. Fig.3(d). Departure from thermal activation behavior Charge ordering, however, is not limited to x=0.5. indicated by the decrease of d In p/dT- around TM Superlattice reflections have also been observed for specimens with 0.21x<O.5. In general, 6 is found to in Fig.2(b) may be related to the incipient magnetic decrease with reducmg X. For x significantly smaller ordering. The most pronounced feature in Fig.2, however, is than 0.5, large fluctuations of 6(< 25%) were observed among different grains. The difference of d In p/dT- that for x=0.5, x sharply drops while the activation energy jumps at To=250 K, pointing to a charge- at 200 K and 300 K shown in Fig.3(c) highlights the ordering transition, as similar anomalies were found increase of the activation energy due to the charge at the charge ordering in 2D nickelates [8]. Direct ordering in 0.251x<O.6. A cusp in x around To-250 evidence for charge ordering is obtained from elec- K also exists in samples with x=0.47 and 0.53. Smaller tron diffraction studies. The photograph in Fig.4 anomalies in x can be detected near To in specimens with x down to 0.05 in the two-phase region (refer to shows an [OOl] zone-axis electron diffraction pattern obtained from a x=0.5 sample at 95 K, well below squares in Fig.3(d)). Unlike the quasi-2D charge ordering observed in the ordering temperature TO.Four sharp superlattice (La,Sr)zNiOJ [8], charge ordering in (Sr,La)zMnOd spots are clearly discernible around each fundamen-

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is a 3D phenomenon. Electron diffraction patterns taken near the [loo] zone-axis also reveal sharp superlattice reflections parallel to the c*-direction. A central difference from the nickelate, however, is the magnitude of the in-plane modulation wave vector. At x=0.5, 6=1/2 for the nickelate, reflecting an alternating occupation of the Ni square lattice by the added holes [8]. The modulation 6=1/4 in the manganate calls for an ordered structure with one ouz of every four Mn sites being occupied by the doped electrons. At x=0.5, this requires two electrons occupying the two dy orbitals of the same Mn ion. Thus there is one row of Mn2+ for every three rows of Mn4+ along the diagonal direction in the Mn square lattice (Fig.4). It has been known that Mn2+ with 3d5 high spin configuration is exceptionally stable [ 181.The energy of Mn2+ (3d)-Mn4+(3d3) configuration is lowered by Hunds rule exchange as compared with equalelectron-numbered Mn3+(3d4)-Mn3+(3d4) configuration. However, Mn2+ is less common in perovskites and related materials due to its large size (r2+=0.838r, r3+=0.65A, r4+=0.53A [19]). Nevertheless, the possibility of 2Mn3+ - Mn2+ +Mn4+ has been suggested in perovskite manganates [20]. To comprehend our experimental findings, we note that doped electrons can only enter 3d, orbitals with their spins parallel to the half-filled 3d, shells. Therefore, it is beneficial to treat the Mn4+(3di) lattice as a background and to focus on doped electrons distributed among 3d, orbitals on this square lattice. The scenario we propose is based on the two possible ways the doped electrons populating the 3d, orbitals. In one case, only one of the two d, orbitals of a site is occupied by a doped electron. Polarons with highspin Mn3+ character are formed by these dy electrons through interaction with the surrounding lattice and background Mn4+ spins. In the other case, two doped electrons occupy both d, orbitals of the site, forming a high spin Mn2+ state. These two 3d, electrons with parallel spins may become polaronic and mobile at high temperatures, as indicated by the disappearance of the long-range charge order above To. They can be viewed as closely bound triplet bipolarons. Bipolarons with larger size and spin are less mobile than polarons, and thus they are more prone to ordering at low temperatures. While the total number of polarons and bipolarons is controlled by the La content, the ratio between them can vary. The formation of a bipolaron against two polarons, driven by Hunds rule on-site exchange, is hindered by the elastic strain energy which the large bipolaron has to pay to expand the underlying lattice. However, two neighboring bipolarons cost less strain

energy than two separated ones, leading to bipolarons clustering. This mechanism can provide the driving force of macroscopic phase separation into bipolaronrich (B) and polaron-rich (P) phases in the range of O<xsO.38. The much larger ionic radius of Mn2+ than that of Mn3+ leads to larger in-plane square sizes for the B phase than for the P phase (see Fig. 1). Inspection of Fig. 1 also provides a further support for bipolaron, since the expansion of a above the two end members at x=0 (Mn4) and x=1 (Mn3+) can be seen as due to Mn2+ formation. Actually, electron diffraction studies at low temperatures of an x=0.2 sample show two kinds of diffraction patterns: one with superlattice spots quite similar to that shown in Fig.4, and the other without superlattice reflections but showing a monoclinic distortion. The former can be attributed to the phase of bipolarons which are of the isotropic Mn2+ character and order at low temperatures, while the later to the P phase, since Mn3+ with 3d4 is a wellknown Jahn-Teller ion. With more bipolarons around, more of them are likely to form. This explains the decline of P phase and the growth of B phase with doping. The above scenario focuses on the interplay of the Hunds rule exchange energy and the lattice strain energy. A complete theoretical treatment needs to consider other factors, such as many-body effects and oxygen p states. A bipolaron model has been applied to BaBiOs system [21]. Nominally tetravalent Bi cations were found to have different valences at different lattice sites experimentally [22]. Singlet bipolarons were proposed to form with the on-site pairing of 6s electrons, which is stabilized by polarizing the oxygen OG tahedra. In summary, Sr2_XLaXMn04 remains nonmetallic with electron doping for O<x10.8. Two phases coexisting in O<xsO.38 are proposed as being composed of polarons and triplet bipolarons, respectively. The stability of the bipolarons is suggested to come from the large on-site exchange energy. The added electrons order with (rr/2,7r/2) modulation for x=0.5 below -250 K and it can be understood as the formation of diagonal bipolaron stripes on the Mn square lattice, in contrast to the polaron ordering of modulation (rr, TT)for Lai.$Go.sNi04. Magnetic order develops below 150 K. After the completion of our study, we received a paper by Y. Moritomo et al. on Srz-,La,Mn04 (0.31~11) [23]. They observe the charge ordering at x=0.5. However they suggest a nickelate-like charge order which we show here not to be adequate. Acknowledgement-We thank C. M. Varma, P. B. Littlewood and T. M. Rice for stimulating discussions.

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REFERENCES

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