Self-organization of epitaxial La0.35Pr0.275Ca0.

375MnO3 manganite nanorods on NdGaO3 substrates

Jiaqing He, Jin-Cheng Zheng, Yimei Zhu, S. Chaudhuri, and R. C. Budhani Citation: J. Appl. Phys. 103, 064304 (2008); doi: 10.1063/1.2899960 View online: http://dx.doi.org/10.1063/1.2899960 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v103/i6 Published by the American Institute of Physics.

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JOURNAL OF APPLIED PHYSICS 103, 064304 2008

Self-organization of epitaxial La0.35Pr0.275Ca0.375MnO3 manganite nanorods on NdGaO3 substrates

Jiaqing He,1,a Jin-Cheng Zheng,1 Yimei Zhu,1,b S. Chaudhuri,2 and R. C. Budhani2
1

Department of Consdensed Matter Physics and Materials Science, Brookhaven National Laboratory, Upton, New York 11973, USA 2 Condensed Matter-Low Dimensional Systems Laboratory, Department of Physics, Indian Institute of Technology Kanpur, Kanpur 208016, India

Received 19 November 2007; accepted 28 January 2008; published online 21 March 2008 We studied the structure, morphology, and growth mechanism of self-organized La0.35Pr0.275Ca0.375MnO3 manganite nanorods grown on NdGaO3 substrates by pulsed-laser deposition. A two-layered structure was revealed: the rst layer, about 120 nm thick, was formed via layer-by-layer two-dimensional 2D growth; the second layer consisted of a three-dimensional assembly of nanorods lying perpendicular to the 2D layer. The nanorods, averaging 50 nm across and 180 nm long, exhibited six crystallographic orientational domains, but only two predominated, both with their b axis lying parallel to that of substrate parallel to the lm normal and with an in-plane a- and c-axis interchange to minimize local lattice mismatch. We consider that the formation of such self-assembled nanorods is related to the StranskiKrastanov growth mode and discuss the associated energy terms of such growth based on density functional theory calculations. 2008 American Institute of Physics. DOI: 10.1063/1.2899960
I. INTRODUCTION

Self-organizing nanostructural oxides have attracted much scientic and technological interest because of their promising dielectric-, electromechanical-, and magneticfunctional properties and their suitability for highperformance applications in nanotechnologies.18 Several self-organizational routes are being investigated for preparing reliable laboratory-scale nanometric devices based on perovskite oxides.17 Two of the most common pathways are i via self-organization driven by interfacial stress originating during heteroepitaxial growth and ii through threedimensional 3D thickness instabilities within ultrathin lms also known as self-patterning caused by the formation of thermally unstable, unfavorable interfaces.8 The Stranski Krastanov growth mode35,9,10 is a well-used engineering approach to promote the self-organized and self-patterned growths of oxide systems at the nanoscale level. The dynamics of growth is occasioned by the systems transition between close kinetic states, wherein states far from the equilibrium remain stable for long periods. Thus, dynamic states, namely, those whose structures and morphologies are induced by the growth modes, may well coexist with kinetic states. Such coexistence would be driven by the competition between different growth mechanisms and the related strain relaxation, both for the particular material system and under the particular epitaxial-deposition condition. The La0.35Pr0.275Ca0.375MnO3 compound, hereafter refer to as LPCMO, is the focus of particular interest due to the rich variety of physical phenomena such as colossal magnetoresistance CMR and charge, orbital, and spin orderings seen in this system. Additionally, there is urgent technologia b

cal challenge to produce a nanometric CMR-based highdensity device.11,2,1315 At room temperature, LPCMO has an orthorhombic structure space group Pnma with lattice parameters a = 5.441 , b = 7.676 , and c = 5.439 Ref. 16 ; at temperatures above 900 C, it is cubic with a = 0.3894 nm.17,18 The crystallographic relation between these two phases can be described as ak bk ck aP M k bP , cP 1

where a, b, and c are unit-cell vectors and the subscripts k and p denote the indices for the orthorhombic and the perovskite primitive cells, respectively. M k is a transformation matrix for the six possible variants k k = A, A , B, B , C, and C , 0 1 1 MA = 2 0 0 1 0 , 1 0 1 1 MA = 2 0 0 , 0 1 1 1 , MB = 0 0 1 2 0 ,

1 0 1 MB = 0 2 1 0 0 1

1 0 1 1 1 0

1 1 0 MC = 0 1 0 2 , 1 0

MC = 0 0 2 . 1 1 0

Electronic mail: jhe@bnl.gov. Electronic mail: zhu@bnl.gov.

These transformation matrices are important for understanding the growth mechanism and are the basis of our analysis of the equivalent nanorods with six different orientations see Figs. 2 and 4 . On the other hand, the substrate NdGaO3 NGO exhibits a similar orthorhombic crystal structure with
2008 American Institute of Physics

0021-8979/2008/103 6 /064304/5/$23.00

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a = 5.499 , b = 7.719 , and c = 5.417 , which can also be considered as a pseudocubic a = 0.3859 nm Ref. 15 with the a and the c axes rotated 45 and b shortened by half. With these lattice parameters, the mismatch between LPCMO and NGO appears very small, at 0.4% the negative sign indicates an in-plane compressive strain ,19,20 i.e., one-fourth of that for LPCMO/ SrTiO3 1.6% and also for LPCMO/ LaAlO3 +1.5% . Lebedev et al.14 have rst reported lamellar two-state conguration in case of La1xCaxMnO3 manganite lms grown on SrTiO3 substrates with large mismatch; in this work, we investigated the straininduced structure and morphology of self-assembled LPCMO thin lms epitaxially grown on NGO substrates with small mismatch. Our structural analysis shed light on the growth modes of the system, suggesting that strain relaxation is responsible for the self-assembled LPCMO nanorods, even with the small driving force of interfacial mismatch stress.
II. EXPERIMENTAL PROCEDURES

FIG. 1. Temperature dependence of resistivity of LPCMO lm normalized with respect to its value at 300 K for both cooling and heating cycles is shown along with normalized magnetization M T / M 300 K measured under FC and ZFC conditions in 1000 Oe eld aligned parallel to the plane of the lm. The vertical arrow marks the insulator-to-metal transition temperature TIM while cooling and the downward arrow indicated the Curie temperature TC.

LPCMO lms were grown on 110 -oriented single crystals of NGO using pulsed-laser deposition PLD technique. We have ablated the surface of a sintered stoichiometric sintered target of LPCMO with a KrF excimer laser operated at 10 Hz with an aerial energy density of 2 J / cm2/pulse. The lms were grown at the rate of 0.16 nm/ s. The oxygen pressure and the substrate temperature during growth were 300 mTorr and 750 C, respectively. Resistivity measurements were carried out on 1 mm wide strips of the lm using standard four-probe technique, while the magnetization was measured using a superconducting quantum interference device magnetometer. For the measurements of dc resistivity, the test current was 10 A at which the maximum power dissipated in the sample due to the Joule heating is 0.05 W. Transmission electron microscopy TEM investigations were performed using a JEOL-3000F microscope.20 TEM samples were prepared by standard mechanical thinning and ion-milling procedures. Both plane-view and crosssectional samples were obtained, and numerous areas were examined using lattice imaging and selected area electron diffraction SAED .
III. RESULTS

The temperature T dependence of the resistivity T , normalized to its value at 300 K, of the LPCMO sample is shown in Fig. 1 left scale . The T is marked by a semiconductorlike behavior on cooling below room temperature, followed by an insulator-metal transition at TIM 180 K as marked by arrow in Fig. 1. The thermal cycle exhibits supercooling and superheating effects, indicating a rst order phase transition. In the right hand side scale of Fig. 1, we show temperature dependence of magnetization M measured with an in-plane eld of 1000 Oe in both the eld cooled FC and zero-eld cooled ZFC modes. Owing to the large paramagnetic contribution from the NGO substrate, the exact value of the magnetic moment of the LPCMO lm cannot be determined. Nevertheless, a qualitative depen-

dence of M on T can be extracted out and is displayed in Fig. 1. The onset of spontaneous magnetic ordering at TC = 190 K is clear from the gure. Figure 2 a is a cross-sectional overview of a 300-nm-thick LPCMO lm on the NGO substrate, showing that the lm consists of a two-layered structure. The rst sublayer, containing dislocations, has a single-domain conguration that extends 120 nm from the LPCMO/NGO interface, whereas the second sublayer encompasses columnar structures with parallel nanorods, each also being a single orientational domain. These columnar rods have a narrow lateral size distribution of about 20 50 nm and are separated by either a crystalline domain boundary, including an antiphase boundary APB , or by a thick amorphous layer, which often has grown out of an APB see Figs. 2 c and 2 b , respectively . The interface between the lm and the substrate appears to be coherent without interfacial dislocations and visible strain contrast Fig. 2 d . Figure 2 e is SAED pattern taken from an area covering sublayer 1 of the LPCMO lm and the NGO substrate. There are two sets of Bragg spots that coincide at low-order reections while being clearly separate at high-order ones. Careful measurements suggest that the lattice mismatch between the substrate and the lm in the a and c directions in plane is about 0.1% and along the b direction out of plane near the substrate is about 2.3%, while near sublayer 2 is about 2.1%. These values signicantly deviate from the mismatch values of the bulk lattice parameters between LPCMO and NGO that we c = 0.6% and b = 0.05% , cited in Introduction1113 a i.e., about four times smaller in plane and larger out of plane. The SAED pattern in Fig. 2 f , taken from a region covering sublayer 1 and sublayer 2 and the NGO substrate, has three sets of reections. Those marked with squares are from the substrate and sublayer 1 domain A , similar to Fig. 2 e , while those marked by circles are from domain A in sublayer 2. The reections marked by the black circles and triangles are forbidden reections, whose weak intensities in Fig. 2 f

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FIG. 2. a Cross-sectional TEM image of LPCMO/NGO showing the twolayer growth of a LPCMO lm on a NGO substrate. A, A , C, and B correspond to the different orientation domains see Eq. 1 in the text . b d Three enlarged images of the boxed areas in a . b and c Two types of domain boundaries in sublayer 2: b an amorphous boundary between two C-orientated domains grown out of an antiphase boundary APB and c an APB between the A and A domains with the Fourier analysis . d The coherent interface between the NGO substrate and the LPCMO lm. e and f SAED patterns e from a region including sublayer 1 of the lm and the substrate and f from both sublayers of the lm and the substrate. Analysis of the splitting of the Bragg spots at high-order reections reveals a 2% lattice mismatch along the b axis and 0.04% along the a and c axes between the lm and the substrate. The circles and squares in f correspond to two orientation variants domains A and A , while the black circles and triangles are due to the double diffraction.

FIG. 3. Color online a Plane-view image of a thin lm showing the rectangular cross section of the nanorods with a thick amorphous layer or an APB as their boundaries. The orientations are marked as the primitive cell. b The corresponding electron diffraction pattern in sublayer 2 also indicates a multidomain structure marked by squares, circles, and diamonds, corresponding to domains A, B, and C, respectively . The schematic of the three reciprocal cells is shown at the right. c Lattice images of domains A, B, and C where the interface between A and B is an APB and that between B and C is a 2-nm-thick amorphous boundary. The Fourier analyses insets show their relative orientation and single-domain structure.

are caused by multiple scattering. Both Figs. 2 e and 2 f are the 100 * zone patterns of the orthorhombic LPCMO/NGO structure, in which the 010 direction is parallel to the direction of the lm normal. Figure 3 a shows plane-view morphology of the projected column structures of the lm. Almost all of them are rectangular, and their edges in the lms plane lie parallel to the 100 p direction of the primary perovskite pseudocubic NGO or to the 010 and 101 directions of the orthorhombic unit cell. The cross-sectional dimension of the columns ranges between 20 and 90 nm, but about 80% are between 30 and 60 nm, suggesting that they have nearly uniform growth with a narrow size distribution. The two types of domain boundaries between adjacent columnar domains are clearly visible; one is a crystalline domain boundary, while the other is lled with a 2 5 -nm-thick amorphous layer Fig. 3 c . Energy dispersive x-ray analysis and electron energy loss spectroscopy revealed that the composition of these amorphouslike layers is almost the same as that of the columnar domains except they are oxygen decient. The SAED pattern Fig. 3 b , taken from an area that included several columns, was characterized by having, besides the fundamental reections, three sets of extra spots, marked by squares, circles, and diamonds the corresponding domains

are denoted as A, B, and C, respectively, in Fig. 3 c , suggesting three different orientation variants. Each column is a single crystal, as evidenced by the corresponding diffractogram.
IV. DISCUSSION

Our results reveal that epitaxial LPCMO lms grown on NGO follow the StranskiKrastanov growth mode, i.e., a two-dimensional 2D growth followed by a 3D growth, as sketched in Fig. 4. This two-step mechanism is mainly driven by the competition between the surface energy and the strain energy of LPCMO/NGO. The free energy of the system can be expressed as
sub film E = E0 + Esurf + Esurf + Einterf + Estrain ,

2
sub Esurf

where E0 is the internal energy of substrate and lm, film and Esurf are surface energies of the substrate and lm, respectively, while Einterf is the interfacial energy between LPCMO and NGO, and Estrain is the mist-strain-induced free energy, including that due to the defects. Since the inplane lattice mismatch of the lm and the substrate is extremely small 0.1% , as measured by our electron diffraction, and the lms were grown at a very slow rate with few

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FIG. 4. Schematic representation of different stages in the structural evolution of an epitaxial LPCMO lm: layer 12D growth mode with a few mist dislocations; layer 2columnar growth arising from the incomplete coalescence of 3D nuclei, each column with a dissimilar domain structure. The plane view corresponds to the viewing direction of Fig. 3, while view 1 and view 2 are the viewing directions of Figs. 2 c and 2 d and Fig. 2 b , respectively.

defects present during the early stage of the growth, we can consider that the system is in an equilibrium thermodynamic state.21 When the sum of the surface energy of the epitaxial lm and the free energy of the lm/substrate is smaller than that of the surface free energy of the substrate, a 2D growth mode prevails, while the opposite case results in 3D growth. To verify whether the 2D growth criterion is fullled, we undertook rst principles full-potential calculations based on density functional theory DFT .22,23 We calculated both the 001 surface and interface energies of the system and obNGO LPCMO tained Esurf = 0.156 eV/ 2, Esurf = 0.133 eV/ 2, and LPCMO/NGO NGO LPCMO 2 Einterf = 0.016 eV/ ; thus, we have Esurf Esurf LPCMO/NGO + Einterf . In other words, creating a new lm surface and an interface with the substrate is energetically favorable at the expense of the same surface area of the substrate. This agrees well with our experimental observations demonstrating that the initial mode is, indeed, a 2D nucleation process followed by layer-by-layer coherent growth layer 1 in Fig. 4 . Although we used unrelaxed geometries in our calculations for the surface and interface, relaxation may slightly reduce the values of the energies, but would not change our conclusion. In this smoothly grown sublayer 1 near the substrate, the strain is relatively small and uniformly distributed due the small interfacial mismatch. Nevertheless, the strain increases with the lm thickness. With the continued buildup of the epitaxial atomic layers during growth, excess elastic-strain energy accumulates, while the strong adhesion exerted by the substrate disappears beyond a critical thickness20 estimated to be 100 nm for our system . As the strain-associated energy rises above that required for the formation of mist dislocations, the lm relaxes partially through the creation of such dislocations thereby causing a reduction in the systems energy. Consequently, the accumulated strain energy will be partly relaxed. However, at the atomic scale, this will introduce local distortions that disrupt the homogeneity of strain elds within a LPCMO lm. Thus, the near-mist dislocation regions are stressed, whereas the interdislocation regions are less stressed or unstressed. With further growth, the adatoms on the lms surface will be transported from the

stressed regions to the unstressed regions through surface diffusion, and eventually, the lm becomes unstable against the long-wavelength corrugation of the surface and forms coherently strained 3D islands, i.e., the 2D growth mode changes to a columnlike 3D mode layer 2 in Fig. 4 . The deposited atoms attempt to nd positions that will dynamically relieve the strain in the lm during growth. The resulting increase of the surface energy is overcompensated for by a decrease in strain energy due to the relaxation of elastic strain toward the bulk lattice constant in the upper parts of the 3D islands. One important aspect of strain relaxation is the creation of local defects, including dislocations and planar defects, such as the amorphouslike domain boundaries or APBs in the regions of coalescence of the islands. A small strain results in crystalline coherent domain boundaries, while a large strain yields disordered amorphous interfaces. Finally, minimization of surface energy leads to the formation of the rectangular columns/rods with low-energy basal planes as their surfaces, along with the formation of ordered arrays by self-organization. We note that the long edge direction of the rectangular rods is not related to a preferred growth orientation, which was determined to be either a, b, or c direction of the lm, but is more associated with the variation of local length scale of the surface corrugation during the growth. We also note that there are six orientation domains in sublayer 2, only two are predominant A and A . This can be mainly attributed to the small in-plane mismatch 0.1% , compared to the other variants 2% for B, B , C, and C when 010 is in plane , and anisotropy of the surface energy.24 Furthermore, In our previous work,11 we point out that the lms grown at a high rate of 0.32 nm/ s possess very few mist dislocations and follow 2D growth mode when other growth conditions are kept the same as in the present case. Although the morphology and structure of the lms were different, the resistivity and magnetization of the lms investigated here are broadly the same as those of high growth rate lms shown as in Ref. 11.
V. CONCLUSION

In summary, we have successfully fabricated selfassembled, ordered arrays of 3D La0.35Pr0.275Ca0.375MnO3 manganite nanorods using PLD. Each nanorod is single, dislocation-free orientational domain, and all nanorods are either encapsulated by thick amorphous boundaries or antiphase domain boundaries. We demonstrated by DFT calculations that the formation of such self-organized coherent columnar nanorods follows the StranskiKrastanov growth mode.
ACKNOWLEDGMENTS

This work at BNL was supported by the U.S. Department of Energy, Ofce of Basic Energy Science, under Contract No. DE-AC02-98CH10886. The IIT-Kanpur Research was funded by the Nanoscience Initiative of the Department of Science and Technology, Government of India.
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