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# Transport and magnetic anisotropy in CMR thin film La1-xCaxMnO3 (𝑥≃1/3) induced by a film-substrate interaction

## I Introduction

Discovery of so called colossal magnetoresistance (CMR) in doped lanthanum manganites of the type La1-xAxMnO3 (where $`A`$ is a divalent alkaline-earth element like Ca, Sr, Ba)  has fundamental importance for solid state physics and offers promissing application in advanced technology. The most pronounced effect of CMR (i.e., an extremely large negative magnetoresistance (MR)) was found in La1-xCaxMnO3 films with $`x1/3`$. In the concentration range $`0.2<x<0.5`$ the La1-xCaxMnO3 is a ferromagnet with a rather high conductivity at temperatures far below the Curie temperature $`T_c`$. The resistance strongly increases with temperature and has a peak at a temperature $`T_p`$ which is close to $`T_c`$ in samples with fairly perfect crystalline structure. The MR is maximal near $`T_c`$. Above $`T_p`$ (in the paramagnetic state) the resistance has semiconducting behavior and the MR is much less. Below $`T_c`$ the MR strongly decreases with decreasing temperature, and it is believed that the MR must go to zero on approaching $`T=0`$ K in fairly good crystals.

The common explanation of the CMR is usually provided in the frame of the double-exchange (DE) model  which is based on the assumption of the appearance of Mn4+ ions with substitution of La3+ by a divalent cation. It is believed that in this case a ferromagnetism results from the strong ferromagnetic exchange between Mn3+ and Mn4+. This model, however, cannot explain the many features of the resistivity behavior of manganites in both the ferromagnetic and the paramagnetic states. Therefore, in succeeding theoretical works additional physical mechanisms (mainly still in the frame of DE model) were considered. The possible influence of strong electron-phonon coupling (Jahn-Teller distortion), polaronic effects (magnetic or lattice polarons), nearly half-metallic nature of ferromagnetism in the manganites, electron localization, phase separation and other effects were considered (see Refs.  and references therein).

In spite of extensive experimental and theoretical efforts a clear understanding of CMR in the manganites is not yet available. The reason is that the knowledge of even the basic electronic properties of doped manganites is still far from complete. For example, one can find in the literature conflicting experimental claims regarding the nature of holes in doped manganites at $`x<0.5`$. The DE model is based on the assumption that the holes in doped manganites correspond to Mn4+ ions arising among the regular Mn3+ ions due to the doping. But some investigations give strong evidence that the holes are located mainly on the oxygen ions  (i.e., the holes are of O $`p`$ character). On the other hand there is experimental evidence (see Ref.  and references therein) that holes doped into LaMnO3 are mainly of Mn $`d`$ character.

One of the important questions in physics of the CMR manganites is the nature of the rather high-conducting state below $`T_c`$. The only sure assumption at present is that the charge carriers at low temperatures can be considered to be quasifree. Whether the doped CMR manganites in the ferromagnetic state should be regarded as conventional bad (disordered) metals or as just heavily doped degenerate semiconductors has been argued . It is known, however, that manganites do not behave like conventional non-ferromagnetic metals. For example, the decrease in resistivity with decreasing temperature of fairly good crystalline manganites is too large to be attributed, as in conventional metals, to the electron-phonon interaction . It follows also from the known experimental data that a clear correlation exists between transport properties and magnetism in doped manganites. Namely, the resistance $`R`$ of manganites in the ferromagnetic state is a function of the magnetization $`M`$ which in turn depends on the temperature and magnetic field: $`R=f[M(T,H)]`$. In manganites the conductivity increases with the enhancement of ferromagnetic order. This is actually the source of the huge resistivity decrease at the paramagnetic-ferromagnetic transition and the CMR. This correlation is most pronounced in good quality crystals, but persists to some degree even in rather disordered systems, like polycrystalline or granular samples.

The bulk manganites La1-xAxMnO3 ($`x1/3`$) have nearly cubic symmetry and therefore should not have any marked MR anisotropy. In contrast, the CMR films possess a pronounced MR anisotropy in low magnetic fields . Due to the above-mentioned transport-magnetism correlation it should be thought that the MR anisotropy in CMR films is in fact some reflection of $`M(T,H)`$ behavior. Two main sources of MR anisotropy in ferromagnetic films are: (1) the existence of preferential directions of magnetization (due to strains stemming from the lattice film-substrate mismatch or other sources), and (2) dependence of resistance on the angle between current and magnetization, which is inherent in ferromagnets (the so called anisotropic magnetoresistance (AMR) effect).

It was found for the CMR films, which are subject to compressive strain in the film plane, that if the easy magnetization axis is parallel to the film plane, an unusual positive MR appears when the magnetic field is perpendicular to the film plane, while for a parallel field the MR is negative. This behavior can be associated with concurrent influence of the above-mentioned anisotropy sources. In this article, we report that MR anisotropy in CMR films can also manifest itself in far more complex and puzzling ways. The object of study was La1-xCaxMnO3 ($`x1/3`$) films prepared by pulsed-laser deposition (PLD) onto LaAlO3 substrates. We found non-monotonic and alternating dependences of the MR on $`H`$ for both the perpendicular and parallel directions of $`H`$ relative to the film plane with $`H`$ perpendicular to the current (preliminary short report about this behavior was presented at LT22). Only in the longitudinal geometry (when $`H`$ is parallel to both the current and the film plane) was the MR always negative, as expected for CMR manganites. This rather complex behavior of MR manifests itself in the ferromagnetic state and has not been reported in previous studies. We will show below that this behavior is determined by a peculiar structural disorder induced by a film-substrate interaction. From the transport and magnetic properties of the film studied, it can be concluded that the film crystal structure should be inhomogeneous in such a way that various parts of the film have non-identical (and quite distinct) magnetic properties. This hypothesis is supported by x-ray diffraction which revealed that the film is inhomogeneous in strains, lattice parameters and lattice orientation. The possible reasons for the formation of such structure and its effect on MR anisotropy are considered. We note that although similar MR behavior was observed for several films prepared by this technique, the detailed measurements reported here were all taken on the same film, a representative specimen.

## II Experiment

La1-xCaxMnO3 ($`x1/3`$) films were grown by PLD on (100) oriented LaAlO3 substrate. A PLD system from Neocera Inc. with a Lambda Physik KrF excimer laser operating at 248 nm was used to ablate the target material with a nominal composition La2/3Ca1/3MnO3. The main details of the target preparation and laser ablation technique are described in Ref. . Stoichiometric amounts of high purity La2O3, CaO and MnCO3 were mixed and ball milled for several hours, reacted at 1100C for 24 hours with intermediate grinding and mixing after 12 hours, and pressed with Duramax B-1020 acrylic binder at 50-170 MPa to make the target pellet. The pellet was sintered at 600 – 1200C for 12 hours in a box furnace in air to burn off the binder and strengthen the pellet. During deposition the pulse energy was 228 mJ with a repetition rate of 8 Hz. The target-substrate distance was about 7 cm.

The film 80 nm thick described in this paper was ablated at a substrate temperature of 400C in an oxygen atmosphere at pressure $`P_{O2}=200`$ mTorr. Time of deposition was about 20 min. Immediately after deposition the film was annealed 30 min at $`T=400^{}`$C in the same PLD chamber at $`P_{O2}=330`$ mTorr. The film was also post-annealed in flowing oxygen for 24 hours at 900C.

X-ray diffraction (XRD) study of crystal-structure of the film and the substrate was done using a DRON-3 diffractometer with a Ge(111) monochromator and CuKα1 radiation. Magnetization and ac susceptibility measurements were done by commercial SQUID magnetometer. Resistance as a function of field and temperature was measured using a standard four-point probe technique. The available cryostat with a rotating electromagnet makes it possible to measure resistance in magnetic fields up to 20 kOe with different directions of $`H`$ relative to the plane of the film and the transport current.

## III Results

### A X-ray diffraction

#### 1 Analysis method

The two methods of XRD study were used: (i) normal $`\mathrm{\Theta }2\mathrm{\Theta }`$ scanning, and (ii) diffractional reflection curve (DRC) recording. DRCs were recorded on symmetric and asymmetric reflections. The technique of sample rotation about the diffraction vector was used. That makes variations of the angle between the surface and incident beam or corresponding reflected one possible up to the critical angle of total external reflection which is about $`1^{}`$. The perfection of crystal structure was characterized by the DRC half-width $`\beta _{1/2}`$. The crystal lattice parameters were obtained by the Bond technique.

#### 2 Substrate characterization

The substrate LaAlO3 (from Coating & Crystal Technology (CCT), Kittaning, PA 16201) was (001) oriented. For determination of lattice parameters $`a_s,b_s,c_s`$ (of the pseudocubic cell) the reflections (400), (330) and (003) were used. It was found that $`a_s=0.37902`$ nm, $`b_s=0.37956`$ nm, and $`c_s=0.37836`$ nm. One can compare these values with CCT data ($`a=0.379`$ nm) or with that from one of the special studies of LaAlO3 single crystals ($`a=0.37896`$ nm). The substrate is characterized by the availability of mosaic crystal blocks and twin structure which are common to LaAlO3. The angles of misalignment of fragments (estimated with use of the asymmetric reflections) range up to 0.2. The magnitudes of $`\beta _{1/2}`$ for these fragments are dispersed between 15 and 120 arcsec for different parts of the crystal. Using the asymmetric reflection (101) enables us to conclude that DRC does not experience any significant broadening even at minimum angles ($`1^{}`$) of reflected beam. This demonstrates that the PLD process in our case does not involve a formation of a damage layer on the substrate surface in contrast to the study of Ref.  where the value of $`\beta _{1/2}`$ for the NdGaO3 substrate was increased by two orders of magnitude, and the damage layer was 1.2 $`\mu `$m thick.

#### 3 Film

The film lattice parameters have been determined from the lines (040), (220) and (022). The in-plane lattice parameters are found to be $`a_f=0.3836\pm 0.0002`$ nm and $`c_f=0.3831\pm 0.0002`$ nm; whereas, the out-of-plane one $`b_f=0.3867\pm 0.0002`$ nm. Hence the film has a tetragonal lattice. The ratio of the out-of-plane lattice parameter to the in-plane ones is about 1.009. Bulk La1-xCaxMnO3 ($`x1/3`$) has a cubic lattice with lattice parameter $`a_p`$ in the range 0.385–0.386 nm. It is thus apparent that the film is in a strained state. In the plane of growth the film is under biaxial compression, but it is under uniaxial tension in the direction perpendicular to the film plane. Such a strain state was observed previously in La1-xCaxMnO3 ($`x0.2`$–0.3) films on LaAlO3 substrates. The effects connected with it will be discussed below.

It follows from the XRD data that the crystallographic substrate plane (100)s (which corresponds to the deposition surface) is parallel to the plane (010)f of the film. The fine-structure parameters were obtained from the analysis of several reflections taking into account the DRC broadening. The $`\beta _{1/2}`$ values for the reflections of (101), (202) and (303) are 0.375, 0.42, 0.56, correspondingly. The values of microblock angular misalignment, $`\delta `$, dimensions of coherent scattering areas, $`L`$, and microdeformation, $`\epsilon `$, are 0.32, 60 nm, and $`9\times 10^4`$, correspondingly.

The DRCs at angles in the range 1–6 were asymmetric. There are reasons to believe that this is caused by superposition of reflections from parts of the film with different lattice parameters, since orientations $`[100]_f[010]_s`$ and $`[100]_f[001]_s`$ are quite possible due to the twin structure of substrate. These XRD data will be used below for explanation of the transport and magnetic anisotropy in the film.

### B Transport and magnetic properties

#### 1 General properties

The transport properties of the film in Fig.1 correspond well to the expected behavior of CMR films . Namely, the temperature dependence of the resistance $`R(T)`$ has a maximum (peak) at $`T_p296`$ K. Below $`T_p`$ a quite sharp resistance drop takes place which corresponds to paramagnetic-ferromagnetic transition that occurs approximately simultaneously with the insulator-metal transition. The resistivity $`\rho `$ at $`T=4.2`$ K was about 375 $`\mu \mathrm{\Omega }`$cm. The ratio of the resistances at $`T_p`$ and 4.2 K, $`R_{295}/R_{4.2}`$, is about 31.4. This fairly large variation of resistance with temperature for a rather disordered doped manganite should be attributed mainly to the strengthening of the magnetic order with decreasing temperature. The magnetic field $`H`$ produces a large decrease in resistance (see the insert in Fig.1). For a measure of the MR we have taken $`\delta _H=[R(0)R(H)]/R(0)`$. It was found that $`\delta _H`$ has its maximum absolute value (about 0.43 at $`H=16`$ kOe) at a temperature $`T_m272`$ K.

The temperature dependences of the magnetization $`M`$ and of the AC susceptibility $`\chi ^{^{}}`$ for different directions of magnetic field relative to the film plane are shown in Figs. 2 and 3. These enable the value of $`T_c`$ to be estimated. Since the magnetic moment is the order parameter at a paramagnetic-ferromagnetic transition, it is quite natural to define $`T_c`$ as the temperature where $`M`$ or $`\chi ^{^{}}`$ starts to increase, when going from high to lower temperatures. In this case (as may be seen in Figs. 2 and 3) the $`T_c`$ value of the film is approximately equal to the value of $`T_p296`$ K.

The nearly identical values of $`T_c`$ and $`T_p`$ are characteristic of films with good enough crystal perfection and fairly large grain size. If $`T_c`$ is defined as the temperature at which $`M`$ comes to a half of the saturation value, or as the temperature of the inflection point in $`M(T)`$, as is sometimes done, the value will appear to be somewhat lower (270–280 K). In any case, however, the value of $`T_c`$ and, especially, $`T_p`$ (which is determined quite unambiguously) seem to be somewhat higher than the corresponding values (260-270 K) for bulk Ca-doped manganites of the same composition ($`x=1/3`$) based on the accepted bulk phase diagram. An increase in $`T_c`$ and $`T_p`$ was found earlier in bulk manganites under hydrostatic pressure or in films with considerable compressive strains due to a film-substrate interaction. The maximal effect of hydrostatic pressure on bulk La1-xCaxMnO3 ($`x1/3`$) causes the increase of $`T_p`$ from $`270`$ K to 290 K, and $`T_c`$ from $`268`$ K to $`285`$ K.

The total bulk strain in this film is highly compressive. Indeed, in this film the volume of the unit cell, $`v_p`$, is equal to $`5.682\times 10^2`$ nm3 which is less than $`v_p`$ for bulk La2/3Ca1/3MnO3 (about $`5.75\times 10^2`$ nm3 provided $`a_p=0.386`$ nm). Moreover, this is also less than previously reported values of $`v_p`$ for La1-xCaxMnO3 films. It was found in preceding studies that $`T_p`$ (and $`T_c`$) increase with decreasing $`v_p`$ in La1-xCaxMnO3 films. For example, it was reported that for a film with x=0.3 and $`v_p=5.725\times 10^2`$ nm3, $`T_p`$ is about 275 K . For the film of Figs.1–3 the unit cell volume is less, explaining its higher $`T_c`$ (296 K).

The strain state of the film is however inhomogeneous. In this case the influence of the Jahn-Teller part of the strain tensor on $`T_c`$ can be taken into account, in principle. The equilibrium lattice parameter in bulk La2/3Ca1/3MnO3 is not known, however, with necessary accuracy for quantitative consideration of this effect.

#### 2 Magnetoresistance anisotropy and AMR effect

According to early studies  the MR value in manganites decreases profoundly (but remains negative) below $`T_c`$ as the temperature is reduced. More recently, it was shown that MR in strained manganite films can be positive at low temperature. We present below a far more complex behavior of $`R(T,H)`$ for this film (Figs. 4–6) which is determined by magnetic anisotropy induced by a film-substrate interaction. In these Figures, as well as in the following text of the paper, we will use designations $`H_{}`$ and $`H_{}`$ for the cases of field $`H`$ applied perpendicular and parallel to the film plane, correspondingly.

Let us consider, first of all, the MR behavior for the cases that the magnetic field is perpendicular to the current. Figs. 4 and 5 present the case for different field orientation ($`H_{}`$ and $`H_{}`$). We will look more closely at the MR behavior at helium temperature. It can be seen, that, for increasing $`H_{}`$, the MR is first negative (at $`H_{}4`$ kOe), then positive (4 kOe $`H_{}12`$ kOe), and then negative again (Fig.4). For increasing $`H_{}`$, the MR is positive below $`H_{}6`$ kOe and negative above it (Fig.5). Anisotropic behavior of this kind occurs only at low temperatures. At $`T>20`$ K the MR is negative for both directions of the magnetic field.

If $`H`$ is parallel to both the current $`J`$ and the film plane, the MR is always negative (Fig. 6). It can be seen from Fig. 6 that MR values differ signicantly for the cases when $`H`$ is perpendicular and those parallel to the transport current. This is because of a pronounced dependence of the resistance on angle $`\theta `$ between $`H`$ and the current $`J`$. One of the measured angular dependences is shown in Fig. 7. It is found that $`R(\theta )`$ at high enough field (more than 8 kOe) can be described fairly well by the relation

$$R(\theta )/R(0)=1+\delta _{an}(T,H)\mathrm{sin}^2\theta ,$$
(1)
where $`\delta _{an}=\{[R(90^{})/R(0)]1\}`$ is some positive parameter. This is a manifestation of the AMR effect, which should be inherent in ferromagnets. In manganite films this effect was previously reported in Refs..

The magnetic field dependence of the AMR parameter $`\delta _{an}`$ at $`T=4.2`$ K is shown in Fig. 8. It can be seen that $`\delta _{an}`$ increases with field in the range below $`8`$ kOe and comes to some saturation value at higher field. This saturation, as will be shown below, proceeds approximately at the field $`H_s`$ where the magnetization comes to rotational saturation in a field perpendicular to the film plane. Some clear inflection in the $`\delta _{an}(H)`$ dependence at $`H2.5`$ kOe can be seen. This inflection should not take place for homogeneous systems (compare, for example, with results of Ref. ) and reflects, as will be shown below, the structural and magnetic inhomogeneity of the film studied.

A temperature dependence of saturated values of $`\delta _{an}`$ is shown in Fig. 9. Three important features of $`\delta _{an}(T)`$ behavior can be derived from the Figure. First, $`\delta _{an}`$ is nearly constant at low temperatures (up to 150 K), where the saturation magnetization of the film does not depend practically on the temperature, as will be shown below. Second, $`\delta _{an}`$ values go up in the temperature range of the ferromagnetic-paramagnetic transition in such way that the $`\delta _{an}(T)`$ curve has a maximum at $`T=280`$ K which is close to $`T_c`$ and $`T_p`$ (see Figs. 1–3). Third, the magnitude of $`\delta _{an}`$ goes clearly to zero at the transition to the paramagnetic state. The latter is quite expected since the AMR effect is unique to the ferromagnetic state.

Let us present now a behavior of the ratio of resistances in magnetic fields perpendicular and parallel to the film plane (we denote these resistances as $`R_{}`$ and $`R_{}`$) in the case that both fields are perpendicular to the current (Fig. 10). In this case the AMR effect has no influence on MR. It can be seen that the ratio of $`R_{}`$ and $`R_{}`$ is less than unity in low field ($`5`$ kOe) and more than unity at higher field with a tendency to saturation at high enough fields. This behavior should reflect the magnetization anisotropy behavior. In Fig. 11 the temperature dependence of the ratio between MR in parallel and that in perpendicular fields, $`\mathrm{\Delta }R_{}(H)/\mathrm{\Delta }R_{}(H)`$, is presented at $`H=15`$ kOe (this field is high enough to saturate the magnetization in any direction, therefore, both the $`\mathrm{\Delta }R_{}(H)`$ and $`\mathrm{\Delta }R_{}(H)`$ are negative). It is seen that MR anisotropy is high below $`T30`$ K. Then, with increasing temperature, $`\mathrm{\Delta }R_{}(H)/\mathrm{\Delta }R_{}(H)`$ decreases to some nearly constant value about 1.3, which persists up to 220 K. It decreases further at higher temperatures, reaching $`1`$ at room temperature, i.e. near the Curie temperature $`T_c`$. Therefore, this type of MR anisotropy is connected with ferromagnetic state as well. This point will be discussed in more detail below.

### C Magnetic anisotropy

The behavior of these MR anisotropy effects suggests that the anisotropy is caused not only by the AMR effect, but that it also results from the magnetization anisotropy. This anisotropy exists in this film as shown in Figs. 2 and 3. It is obvious from these Figures that the film is magnetized more easily in the field direction parallel to the film plane. To check more thoroughly, we have measured $`M(H)`$ in the both directions at different temperatures in the range 4–100 K in fields up to 20 kOe. We have found that the saturation magnetization $`M_s`$ essentially does not depend on the temperature in this range ($`M_s`$ is lowered only by a few percent after warming from 4 K to 100 K). The $`M(H)`$ dependences are observed to be quite different for the field directions parallel and perpendicular to the film plane, but for the same field direction the recorded $`M(H)`$ curves for different temperatures practically merge together. Only in the low fields ($`0.5`$ kOe in the parallel direction and $`2.5`$ kOe in the perpendicular direction) can differences be found between the low and high temperature behavior. To consider this and other effects more properly, Fig. 12 shows $`M(H)`$ dependences for $`T=4`$ K and 100 K. These two graphs illustrate low temperature (below 30 K) and high temperature (above 50 K) peculiarities of $`M(H)`$ behavior for this same film. First of all, it should be noted, that experimental points in these graphs present the data recorded for increasing and subsequently for decreasing applied magnetic field. No significant hysteresis in the $`M(H)`$ curves at low temperature and only a rather weak one at high temperature in weak fields can be seen. Second, there is a pronounced difference in the $`M(H)`$ curves recorded for parallel and perpendicular directions of the magnetic field, which provides an unquestionable evidence of the magnetization anisotropy. The $`M(H)`$ curves for both field directions are rather extended (therefore, it can be argued that neither represents the easy magnetization axis), but it is, however, clear that, on the whole, the film is magnetized more easily in the parallel field direction.

One more difference can be seen from comparing the two graphs in Fig. 12. Namely, at low temperatures it appears as if the magnetization is nonzero and rather high at zero field for both field directions \[Fig. 12 (a)\]. For increasing field, the magnetization increases, however, rather slowly. By contrast, at high temperatures the magnetization increases with the field more gradually, beginning from zero, without any peculiarities in low fields \[Fig. 12 (b)\].

It should be recognized, however, that true zero magnetic field cannot be set in the magnetometer. For experimental reasons there is always some stray magnetic field of the order of 1 Oe. This weak field is sometimes quite enough to cause a significant magnetization at nominal $`H=0`$ in the case of low coercivity. The $`M(H)`$ behavior shown in Fig. 12 (a) suggests that, at low temperatures for both perpendicular and parallel field directions, some parts of the film have a very low coercivity (this causes the jump-like increase in the magnetization in very low fields); whereas, other parts of the film have a higher coercivity. In other words, it can be argued that some parts of the film have a substantial in-plane magnetization; whereas, other parts have a substantial out-of-plane magnetization for a magnetic field which is very close to zero. This is an evidence that the demagnetization energy at low temperatures cannot overcome entirely the spontaneous (parallel and perpendicular) magnetization in some (different) parts of the film. This effect is not pronounced at higher temperatures ($`T>50`$ K) \[Fig. 12 (b)\].

It should be noted, that some features of the magnetic-anisotropy behavior of this film correlate well with its MR behavior. It follows from Fig. 11, that the absolute values of negative MR in parallel field are greater than those of in the perpendicular field ($`\mathrm{\Delta }R_{}(H)/\mathrm{\Delta }R_{}(H)>1`$). Since the conductivity of manganites increases with an enhancement of the magnetic order, this behavior just reflects the point that the magnetization increases more easily in a magnetic field parallel to the film plane. This MR anisotropy is connected with the ferromagnetic state. For this reason it disappears when $`T`$ approaches $`T_c`$ (Fig. 11).

## IV Discussion

In this Section we will discuss the different sources of MR anisotropy in ferromagnets (FM) and their possible effects in this film. We will not consider here the influence of ballistic mechanisms of the MR and MR anisotropy in FM , which are connected with the curving of electron trajectories in a magnetic field. These are important only if the electron mean-free path is fairly large, which is not the case in rather resistive manganites. The AMR effect which is an intrinsic source of MR anisotropy in any FM will be considered as the first point. This effect plays a crucial part in the MR anisotropy of the films studied. As the last but not least point, the extrinsic or induced sources of MR anisotropy which are caused by the shape and strain state of the FM will be thoroughly discussed. These are especially important for films and small particles. It will be shown that the rather complicated MR anisotropy behavior found in this film can be explained by the concurrent influence of these intrinsic and extrinsic sources of MR anisotropy.

### A AMR effect

This effect in ferromagnets is thought to be caused by the spin-orbit interaction (see Refs.  and references therein). The known theoretical models are related to 3$`d`$ metals such as Ni, Co, Fe and its alloys. Some attempts to apply the similar model concepts to manganites were made in Ref. . It can be said at the moment, however, that mechanisms for AMR in manganites are not clearly understood. From the other side, the essential features of this effect in manganites are already established rather well. The temperature dependence of the AMR parameter $`\delta _{an}(T)`$ recorded in this study (Fig. 9) corresponds well to previous results. Among other factors, the most important features of $`\delta _{an}(T)`$ behavior such as the constancy the magnitude of $`\delta _{an}(T)`$ at low temperatures ($`TT_c`$), the maximum in $`\delta _{an}(T)`$ at $`TT_c`$, and the approach to zero of $`\delta _{an}(T)`$ at $`T>T_c`$, correspond to the above-mentioned results.

There is no clear notion among scientists at present as to which factors determine the magnitude of the AMR effect in manganites. Most of the authors usually refer to behavior of 3$`d`$ metals and the corresponding theories developed for these metals. But this approach does not appear to be very fruitful. Indeed, it follows from the 3$`d`$-metal models that the AMR parameter $`\delta _{an}`$ should depend somehow on the magnetization. Really, the AMR effect takes place only in ferromagnets with a spontaneous magnetization. After the transition to the paragmanetic state, and the disappearence of the spontaneous magnetization, $`\delta _{an}`$ goes to zero. But no clear correlation between the AMR amplitude and the saturation magnetization was found for 3$`d`$ metals. Thus this type of general explanation about the influence of magnetization is not very productive for understanding the AMR effect in manganites. Let us consider an other example. It was experimentally found for 3$`d`$ metals (with corresponding theoretical support) that $`\delta _{an}`$ is proportional to $`T_cT`$ on approaching the Curie temperature from below. This means a linear decrease in $`\delta _{an}`$ to zero when $`T`$ approaches $`T_c`$. But this is clearly not the case for manganites where $`\delta _{an}(T)`$ has a maximal amplitude near $`T_c`$ (see Fig. 9 of this paper and corresponding Figures in Refs. ). Therefore, the AMR behaviors of manganites and 3$`d`$ metals are drastically different and must be governed by different mechanisms.

Upon a closer view of results of this study together with these of Ref.  a clear correlation between the magnitudes of $`\delta _{an}`$ and MR in manganites is revealed. This correlation is rather apparent, but, surprisingly, was never mentioned in preceding papers. Indeed, the temperature dependence $`\delta _{an}(T)`$ is entirely analogous to the MR temperature dependence (see insert in Fig. 1 or similar graphs in the numerous CMR papers, for example, in Refs. ). The MR in the CMR manganites has some minimal magnitude at $`TT_c`$, goes to maximal value near $`T_c`$, and approaches zero at $`T>T_c`$ in the same manner as the AMR parameter $`\delta _{an}(T)`$ (Fig. 9). It should be noted that this type of temperature behavior of $`\delta _{an}(T)`$ and MR is a feature of manganite samples with fairly good crystal perfection only. In disordered doped manganites (for example, in polycrystalline or granular samples), the MR can rise with decreasing temperature. In that case, as shown in Ref. , the parameter $`\delta _{an}`$ increases with decreasing temperature as well.

As was mentioned above, the resistance $`R`$ of manganites in the ferromagnetic state is a function of magnetization. The conductivity increases with enhancement of ferromagnetic order. This is the source of the huge negative MR in manganites. The MR magnitude is determined by the ability of an external magnetic field to increase the magnetization. It is obvious that in good crystals at low temperature ($`TT_c`$), when nearly all spins are already aligned by the exchange interaction, the ability to increase the magnetization in the magnetic field is minimal. For increasing temperature and, especially, at temperatures close to the Curie temperature $`T_c`$, the magnetic order becomes weaker (the magnetization goes down) due to thermal fluctuations. In this case the possibility to strengthen the magnetic order with an external magnetic field increases profoundly. This is the reason for maximal MR magnitude near $`T_c`$. At last, above $`T_c`$, the spin arrangement becomes essentially random, the magnetization is zero, and, the MR is close to zero as well. From the aforesaid, it might be assumed that the magnitude of the AMR effect in CMR manganites is determined by the same factors, as that of the MR, namely, by the possibility to increase the magnetic order by an applied magnetic field. This feature must be important for further determination of the nature of the AMR effect in CMR manganites.

One further comment must be added. To see the AMR effect properly, the magnetization should be parallel to the applied magnetic field. That is, the magnitude of the field must be high enough to saturate or rotate the magnetization to the selected direction. In other words, the applied field should be sufficient to overcome the different anisotropy energies of the film. Actually, the $`\delta _{an}(H)`$ behavior should reflect somehow the magnetization curve $`M(H)`$ in the direction perpendicular to the film plane, and, hence, reflect the influence of the available anisotropy sources. As indicated above in Sec. III C, the recorded $`M(H)`$ curves at low temperature ($`TT_c`$) \[Fig. 12 (a)\] indicate that some parts of the film have a substantial in-plane spontaneous magnetization, while other parts have a substantial out-of-plane one in a magnetic field which is very close to zero. We believe that the inflection in the $`\delta _{an}(H)`$ dependence (Fig. 8) at weak fields reflects this magnetization inhomogeneity in this film.

### B Extrinsic MR anisoropy sources and their interplay with the AMR effect

It is known that FM consists of magnetic domains which are regions of spontaneous magnetization. Therefore, even in the absence of an external magnetic field the electrons in FM feel the internal magnetic field $`B=M_s`$. For this reason, any measured resistance for a FM is, in fact, some measure of its MR as well. Apart from the influence of the intrinsic field, there are additional specific mechanisms of electron scattering in FM metals. Let us call them the “magnetic” mechanisms of electron scattering. These can give a considerable contribution to the resistivity and MR of FM metals. In the Matthiessen-rule approximation it is possible to write down for the resistivity of FM metal

$$\rho (T,𝐇)=\rho _{nm}(T,𝐇)+\rho _m(T,𝐇),$$
(2)
where $`\rho _{nm}`$ is the “non-magnetic” part of the resistivity, which is stemming from the usual electron-scattering mechanisms common to non-magnetic metals (scattering on impurities, phonons and so on), and $`\rho _m(T,𝐇)`$ represents the “magnetic” part of the resistivity.

It has been long inferred that the behavior of $`\rho _m(T,𝐇)`$ is some reflection of the temperature and magnetic field dependences of the magnetization. With a rise of magnetization at the transition into FM state, $`\rho _m`$ drops sharply. In the FM state the “magnetic” resistivity is quite small and, in the limit, goes to zero or to very low values for ideal magnetic order. The external magnetic field enhances the magnetic order, that leads to a decrease of resistivity. That is why FM metals are characterized by a negative MR. Of course, at finite temperatures there are some thermal disturbances of the long-range magnetic order (spin waves or magnons) which can determine the power-law temperature dependence of $`\rho _m`$ at low temperatures: $`\rho _mT^n`$, where $`n`$ value depends on the specific mechanism of disturbance.

The known behavior of $`\rho _m`$ in FM metals indicates, therefore, that the influence of magnetic order (or a magnetic lattice of spins) on electron transport is quite similar to that of the crystal lattice order. If the crystal lattice is ideal, the resistance is zero. The same is true (at least, to some significant degree) in respect to magnetic order: for an ideal spin alignment the “magnetic” resistivity may be thought to be equal to zero. Any deviations from long-range magnetic order lead to electron scattering. Just as for crystals, disorder may be static or dynamic disturbances (defects) in the spin lattice. It follows from all this that the “magnetic” part of the resistivity, $`\rho _m`$, is a direct function of the magnetization, that is

$$\rho _m=f[M(T,𝐇)],$$
(3)
The relevant experimental dependences (and its theoretical justifications) for mangnites can be found in Refs. . Lastly, the thermodynamic fluctuations of magnetic order should be mentioned. They are especially strong near the Curie temperature, and, therefore, behavior of $`d\rho /dT`$ and sometimes that of resistivity (as in the case of manganites) has peculiarities at $`TT_c`$.

It should be noted in this place that the “magnetic” and “non-magnetic” contributions to the resistivity cannot be considered as entirely independent. The lattice defects and deviations from magnetic order can be coupled rather strongly and be interdependent. For example, crystal lattice defects, such as grain boundaries, surface regions of film and others, induce disturbances in the magnetic order as well. On the other hand, the changes in the magnetic order, such as development of spontaneous magnetization at the paramagnetic-ferromagnetic transition or moving and disappearence of domain walls in an external magnetic field, can cause a response of the crystal lattice (for example, changes in the elastic stresses and strains).

In explanation of the results of this study it is helpful, as a first step, to consider and keep in mind some known simple cases of the MR anisotropy in manganite films. An instructive example can be found in Ref.  for films La0.7Ca0.3MnO3, grown by molecular beam epitaxy on SrTiO3 substrates. The films were between 50 and 150 nm thick. The authors of Ref.  have studied $`R(H)`$ dependences for the cases where the magnetic field was applied parallel or perpendicular to the film plane. For the perpendicular field direction a positive MR was observed at low fields, which changed to negative one at higher fields. The in-plane MR was only negative and depended on the angle, $`\theta `$, between transport current and field according to Eq. (1), which has been attributed to the AMR effect. The experimental dependences of $`M(H)`$ revealed anisotropy, which is favorable for the in-plane magnetization. Similar results were reported also for Pr0.67Sr0.33MnO3 films deposited on SrTiO3 substrates.

At first glance a positive MR in manganites appears to be quite impossible. Really, the external magnetic field can only strengthen the long-range magnetic order, and, therefore, should lead to decreasing resistance. Nevertheless, it turns out that a concurrence of surface (or shape) anisotropy and the AMR effect can cause the positive MR in a perpendicular field. A comprehensive explanation of this effect can be found in Ref. , so we will restrict ourself only to the main points, which are necessary to understand the observations of this study. An essential prerequisite is that the MR of manganites be determined by the dependence of the magnetization on magnetic field. Assume now that field $`H_z`$ is applied perpendicular to the film plane. At $`H_z=0`$ the magnetization vector $`𝐌`$ has an in-plane orientation (due to the influence of surface anisotropy and the demagnetization energy). At low values of $`H_z`$ the applied field is actually perpendicular to $`𝐌`$. For increasing $`H_z`$ the magnetization begins to rotate so that a component $`M_z`$ appears which is perpendicular to the film plane. As this proceeds the absolute magnitude of the magnetization remains unchanged up to the moment when $`H_z`$ reaches some field $`H_s`$ at which rotational saturation of the magnetization of the film in perpendicular direction takes place. The constancy of the absolute value of the magnetization during the rotation means that the “magnetic” part of resistivity, which depends on $`M`$, remains constant during the rotation as well. In this case it should be expected that the MR would be zero up to the field $`H_s`$. Above this field a further increase in $`H_z`$ results in increasing $`M`$ and, therefore, in a decreasing resistivity. However, instead of this, a positive MR was observed in low fields, and the negative one in higher fields. What is the reason for this behavior?

The point is that the MR is affected also by the AMR effect (that is, by dependence of MR on the angle between the current and magnetization). At $`H_z=0`$ the magnetization vector lies in the film plane. In the explanation of Ref.  it was implied that the current at $`H_z=0`$ is parallel to the magnetization. Maybe this is not rigorously correct, but it is not so important, if an effective angle between $`𝐌`$ and $`𝐉`$ is fairly small. For increasing $`H_z`$, the magnetization vector rotates, that is the angle between $`𝐌`$ and the current increases. This leads to the resistivity rise \[see Eq. (1)\] and is the cause of the positive MR. The magnetization $`𝐌`$ becomes perpendicular to the film plane at $`H_z=H_s`$. At $`H_z>H_s`$ the magnetization begins to increase and this leads to the resistance decrease. As a result of this kind of concurrence the dependence $`R(H)`$ with a maximum takes place. In the parallel field the influence of AMR effect can be thought as absent, therefore only the decrease in resistance in magnetic field inherent for CMR manganites is observed.

The results presented in this paper are quite different from these of Refs. . First of all, in the range of low magnetic field (Figs. 4–6), for a perpendicular field, $`H_{}`$, we found the negative MR in low field, before going to positive MR at higher fields (Fig. 4). At the same time, in a parallel field, $`H_{}`$, a positive MR is seen before becoming negative at higher fields (Fig. 5). This behavior is quite challenging and puzzling. One of the most reasonable explanations for this is an inhomogeneous strain state of the film, that leads (due to the magnetoelastic interaction) to a difference in the magnetic properties (for example, in directions of easy magnetization) in different parts of the film. This turns out to be a basis for understanding of results of this study. The sources of internal strains and stresses in PLD films are quite common and sometimes inevitable due to the lattice film-substrate mismatch. It is just these strains which can be the primary source of inhomogenenous magnetic state of the film studied.

It follows from the known studies that magnetostriction in manganite films (at least with composition La-Ca-Mn-O and La-Sr-Mn-O) is positive. In this case, the magnetization orients parallel to the tensile stresses and perpendicular to the compressive stresses. For fairly smooth substrates, which make possible coherent epitaxy, the in-plane film strain depends on the lattice film-substrate mismatch. If the mismatch is not too large, it can be expected that the in-plane lattice parameters will match those of a substrate and the out-of-plane parameter will be elastically modified according to the Poisson ratio. In this case, a biaxial strain is induced in the film plane which can be tensile or compressive depending on the ratio the substrate lattice parameters and those of the bulk target from which the film is deposited. This is true up to some critical thickness, above which misfit dislocations appear at the film-substrate interface to relax the strain. In that case, film lattice parameters become closer to those of bulk sample.

The above-described scenario is just a generally accepted model which allows some crude predictions to be made. XRD and other studies are required for any specific film-substrate system to know exactly its strain state. Such studies have been done in some studies of the MR anisotropy in doped manganite films. For example, it was found that the La0.7Ca0.3MnO3 films on SrTiO3 substrate studied in Ref.  have in-plane tensile strain, that causes the in-plane magnetization and the appearence of positive MR in the field perpendicular to the film plane. In that case the perfect matching of the in-plane lattice parameters of film and substrate was found. A different example (compressive strain Pr0.67Sr0.33MnO3 films) is described in Ref. . In this case the compressive strains cause the easy magnetization axis to be perpendicular to the film plane. It looks like that in the films, studied in Refs. , the strains, which are induced by the film-substrate interaction, were extended over the most of the film thickness. Consequently, the films in those studies can be considered as nearly (or to a great extent) homogeneous. This is especially true in respect to Ref.  where the film thicknesses were between 7.5 and 15 nm.

For the La1-xCaxMnO3 ($`x1/3`$) film in this study, grown on LaAlO3, the substrate lattice parameters are less than those of the corresponding bulk sample. Therefore, a compressive biaxial strain in the film plane, and a corresponding tensile uniaxial strain in direction perpendicular to the film plane should be expected. This strain state has been actually observed (see Sec. III A). A perfect matching of the in-plane lattice parameters of film and substrate was not found, which is in agreement with the study of La-Ca-Mn-O films on LaAlO3 in Ref. . This is because of partial relaxation of the strain emposed by the substrate. Additionally, the XRD data indicate that the crystall structure of the film is inhomogenenous. It consists of the regions with different crystallographic orientations (see Sec. III A). The origin of the inhomogeneous structure is probably connected with the twin structure of the substrate. As a result, in both the in-plane and out-of-plane directions tensile and compressive regions can be found.

The inhomogeneous film structure reveals itself in the behavior of $`M(H)`$ curves \[see (Fig. 12) and the discussion in Sec. III C\] as well as in the magnetic field dependence of the AMR parameter (Fig. 8) (in the last case we mean the inflection in the $`\delta _{an}(H)`$ curve which should not occur for a homogeneous system). The film inhomogeneity is a key to understanding the observed MR anisotropy (Fig. 4 and 5) as well. It can be assumed that the film is some mixture of regions with different strains. The size of the regions (according to the XRD data) is comparable with the film thickness. The regions with the in-plane compressive strains favor the out-of-plane magnetization in zero field; whereas, the ones with the in-plane tensile strains favor the in-plane magnetization. In the following text we can conveniently speak about the “compressive” and “tensile” parts of the film. In spite of the fact that some part of the film is prone to the out-of-plane magnetization, the influence of the shape anisotropy may cause the total film magnetization to be in the film plane in zero magnetic field or to be canted, as was found, for example, in La-Sr-Mn-O films under compressive stress. In any case, however, it is possible to understand the appearence of a negative MR in low perpendicular fields, $`H_{}`$, (Fig. 4) for an inhomogenenous film of this type . The “compressive” part of the film can be magnetized in the perpendicular direction at very low magnitude of $`H_{}`$ up to the rotation saturation value, and after this the absolute value of magnetization begins to increase with increasing magnetic field. This leads to a resistance decrease, that is, to a negative MR. At the same time, the magnetization of the “tensile” part of the film is in the film plane at zero field and cannot be rotated so easily in the field direction. Considerably higher fields are needed for it. Therefore, at higher fields the explanantion given in Ref. , which takes into accont the AMR effect, is quite applicable to justify the positive MR at higher fields. All these combined effects can produce the observed rather complicated $`R(H_{})`$ dependence (Fig. 4).

Let us turn now to Fig. 5 which represents the behavior of the resistance in a magnetic field, $`H_{}`$, parallel to the plane of the film. In this case the resistance goes up initially for increasing field, but then goes down in higher field. That is, the change in the MR sign (from positive to negative) takes place. To understand this, it should be recalled that both, $`R(H_{})`$ and $`R(H_{})`$, dependencies (Figs. 4 and 5) were registered in magnetic fields perpendicular to the current. At low magnitudes of $`H_{}`$, however, the film magnetization is definitely not perpendicular to the current. At least in the “tensile” regions of the film with the magnetization easy axis parallel to the film plane, the magnetization is by no means perpendicular to the current. The vectors $`𝐌`$ in these regions should have some spread in directions due to the demagnetization energy. Only for increasing $`H_{}`$ do these vectors become strictly perpendicular to the current. Since MR is maximal when the magnetization is perpendicular to the current due to the AMR effect (Fig. 7), the in-plane rotation of magnetization in low fields $`H_{}`$ leads to an increase in resistance. This explains the positive MR for small parallel fields. After aligning the spins in the “tensile” regions parallel to magnetic field, the magnetization begin to increase which causes as usual the resistance decrease. It should be mentioned that a similar effect was observed in Ref.  for a La0.67Sr0.33MnO3 film for magnetic fields applied in the film plane. They found a positive MR for $`HJ`$ as opposed to the negative one with $`HJ`$. $`R(H)`$ curves were measured, however, only in low fields ($`H<1.5`$ kOe), which thus excludes a comparison with the data of this paper (registered in fields up to about 20 kOe).

In fields parallel to both, the current $`J`$ and the film plane, only the negative MR is found in this study (Fig. 6). This is quite expected, since there are no mechanisms for positive MR in this case.

## V Conclusion

The MR behavior in the PLD manganite films can differ dramatically from that of bulk samples. This is due to a film-substrate interaction, which determines the structural and magnetic state of the films. Some film-substrate combinations can lead to rather complicated and puzzling MR behavior for different directions of the magnetic field relative to the film plane and the transport current. To understand such cases properly, one needs to have enough data about the structural and magnetic properties of the films. The MR and MR anisotropy of such film systems depends on the existence of preferential directions of magnetization (due to the strains arising from the lattice film-substrate mismatch and other sources), and from the AMR effect. We have presented in this paper an example of complicated behavior of the low-field MR and MR anisotropy for La1-xCaxMnO3 films on LaAlO3 substrates, and demonstrated how it can be understood.

Based on the results of this study together with the known results of other authors, we have indicated fairly conlusively (and for the first time) that a clear correlation exists between the magnitudes of the AMR effect and MR in manganites. This suggests that the AMR effect in manganites is determined by the ability of the magnetization to increase in an external magnetic field. This important correlation can be helpful in further disclosing the nature of the AMR effect in CMR manganites.

###### Acknowledgements.

The authors are indebted to Dr. N. V. Dalakova for help in measuring $`R(T)`$ dependence in zero magnetic field and Dr. J. H. Ross for his efforts in measuring of film thickness by AFM. Support at TAMU was provided by the Robert A. Welch Foundation (grant A-0514) and THECB ARP 010366-003. BIB and DGN acknowledge support by NATO Scientific Division (Collaborative Research Grant No. 972112).