JP2005213078A - Perovskite manganese oxide thin film, switching element having the same, and method for producing the thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charge-orbital alignment perovskite manganese oxide thin film with which switching characteristic equal to that of a bulk single crystal can be obtained by a polycrystalline thin film; and to provide a switching element having the same and a method for producing the thin film. <P>SOLUTION: An Nd<SB>0.5</SB>Sr<SB>0.5</SB>MnO<SB>3</SB>film is formed on an SrTiO<SB>3</SB>single crystal substrate in which the plane orientation is (110) by a laser ablasion method. Thereby, the charge-orbital alignment perovskite manganese oxide thin film whose crystal lattice orients in the direction parallel to the surface of the substrate and (001) plane being a charge-orbital alignment face is perpendicular to the surface of the substrate is formed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a perovskite manganese oxide thin film (charge orbital aligned perovskite manganese oxide thin film) exhibiting charge alignment and electron orbital alignment, a switching element including the thin film, and a method for manufacturing the thin film.

  In recent years, digitalization of broadcasting and communication has made remarkable progress. Accordingly, a storage device (storage device) capable of handling a wide-band and large-capacity information such as a high-quality moving image has attracted attention. In addition to the spread of magnetic disk memory and optical disk memory, mainly for stationary products, it can be installed in small portable products such as notebook computers, PDAs (Personal Digital Assistants), mobile phones, and even wearable computers. A large-capacity solid-state memory device (nonvolatile memory) is being developed.

  For example, according to Non-Patent Document 1, MRAM (Magnetic RAM) and RRAM (Resistance RAM) are attracting attention as next-generation nonvolatile memories capable of high-speed access similar to DRAM (Dynamic Random Access Memory). In particular, the multi-value approach has become an important technology from the viewpoint of cost because the capacity of the nonvolatile memory element can be increased without relying only on the miniaturization technology.

  In order to realize multi-value processing, it is necessary to store information by a write signal corresponding to multi-value, and to secure a margin capable of sufficiently discriminating each information at the time of reading. That is, there is a strong demand for the development of a new material that can obtain a huge resistance change at a high speed that cannot be achieved with semiconductors.

  As such a material, for example, there is an oxide perovskite single crystal material containing manganese (Mn) as disclosed in Patent Documents 1 to 3.

An oxide perovskite single crystal material containing manganese (Mn) exhibits a huge resistance change of several orders of magnitude when an external field is applied. That is, by applying a magnetic field or a voltage to the antiferromagnetic charge alignment insulating phase in which Mn ³⁺ ions and Mn ⁴⁺ ions are aligned, or by irradiating light, the antiferromagnetic charge alignment insulating phase collapses and antiferromagnetic A switching phenomenon (with a lattice change of several percent) is obtained that transitions from a magnetic insulator (charge aligned state) to a ferromagnetic metal. This is the principle of resistance change in the oxide perovskite single crystal material.

  Recent studies have also reported that the 3d electron orbitals of manganese (Mn) are ordered along with charge alignment. In this specification, the state in which the 3d electron orbits are ordered together with the charge alignment is referred to as charge orbit alignment or charge orbit order, not simply charge alignment.

  In order to realize the switching phenomenon using the charge orbital order in the form of a thin film necessary for device formation, the lattice change accompanying the switching becomes important. The reason is that in a single crystal thin film coherently grown on a substrate, since the in-plane lattice of the thin film is clamped to the substrate, lattice deformation does not remain and phase transition is suppressed.

In addition, the substrate strain is introduced by lattice mismatch (lattice mismatch) between the thin film and the substrate, so that the electrical, magnetic, and optical characteristics of the thin film are changed through modulation of orbital order. For example, in the Non-Patent Document 2, the present inventors have found that the charge-orbit alignment phase is caused by the extension strain acting in the charge-orbit alignment plane (the plane in which charges are aligned and the 3d-electron orbit is also ordered). The stabilization is demonstrated using a Cr _0.5 doped Pr _0.5 Ca _0.5 MnO ₃ thin film. Therefore, in order to facilitate switching with lattice change, it is necessary to manufacture a thin film in which the lattice is relaxed from the substrate (the lattice change is not easily affected by substrate distortion).

  On the other hand, in the thin film (polycrystalline film) relaxed from the substrate (lattice change is less susceptible to substrate distortion), defects are introduced in exchange for relaxing the lattice from the substrate. For this reason, in order to control the switching characteristics by charge orbital order, it is important to determine the influence of defects.

For example, in the non-patent document 3, the present inventors use Pr _0.5 Ca _0.5 MnO ₃ doped with 1% of Cr, and use a substrate and a thin film (Pr _0.5 Ca _0.5 Mn _0.99 Cr). (101) orientation film is produced on an MgO (001) substrate (MgO substrate having a crystal orientation of (001)) having a large lattice constant mismatch with _0.01 O ₃ ) of 10% or more. Magnetic and electrical properties are obtained. The reason why such characteristics are obtained is that the charge trajectory alignment plane forms an angle of 45 degrees with respect to the substrate plane in the (101) orientation film, and therefore the charge trajectory order and the lattice deformation associated with the switching occur on the film plane. Because it occurs both in the film thickness direction, anisotropic lattice deformation is possible with respect to the charge trajectory alignment plane, and it is thought that there are fewer defects in the film thickness direction than in the in-plane direction. It is conceivable that a domain having a thickness of at least the charge orbital alignment phase can be grown.

In addition, in the non-patent document 4, the present inventors manufactured a (001) oriented film completely relaxed on an MgO (001) substrate using Pr _0.65 Ca _0.35 MnO ₃ , Similarly, it shows that sharp switching can be realized.
Japanese Patent No. 2687721 (Japanese Patent Laid-Open No. 8-133894 (publication date May 28, 1996)) Japanese Patent No. 2812913 (Japanese Patent Laid-Open No. 9-249497 (published on September 22, 1997)) Japanese Patent No. 2812915 (Japanese Patent Laid-Open No. 9-263495 (publication date: October 7, 1997)) Nikkei Microdevices January 2003 p.72-83 Appl. Phys. Lett. Vol. 78, p. 3505 (2001) Appl. Phys. Lett. Vol.80, p.1031 (2002) Spring 48th Applied Physics-related Joint Lecture Proceedings 30a-V-11 (2001)

However, the stability of the charge orbital order with respect to the random field caused by the defect differs depending on the material. For example, in a material in which the charge orbital alignment phase is stable with respect to a wide hole doping concentration x, such as Pr _0.5 Ca _0.5 MnO ₃ , the charge orbital alignment phase is charged even if the long-range order of the charge orbit alignment phase is broken. Since the orbital order itself remains, a two-phase coexistence state with the ferromagnetic metal phase can be obtained.

On the other hand, from the viewpoint of switching characteristics in which a larger change is required with a smaller input (low threshold), a substance in a state near the critical point is important because various orders compete. For example, a material in which a charge orbital alignment phase exists only for a very narrow hole doping concentration x, such as Nd _1-x Sr _x MnO ₃ (x = 0.49 to 0.51), is more important. Become.

However, such a material has a strong influence of random potential due to defects on switching characteristics. For example, in Nd _1-x Sr _x MnO ₃ (x = 0.49 to 0.51) manufactured on an MgO (001) substrate, a (00l) oriented film is obtained, but Pr ₀ that is also (00l) oriented. _In contrast to the _.65 Ca _0.35 MnO ₃ film, the charge orbital order almost disappears, resulting in a ferromagnetic phase, and thus a switching effect cannot be obtained. That is, the charge orbital alignment phase itself collapses due to defects.

For example, in the case of Pr _0.5 Ca _0.5 MnO ₃ described above, even if a (101) orientation film can be manufactured on an MgO (001) substrate, a domain is introduced because the substrate surface is isotropic. It becomes difficult to completely align the in-plane orientation. For this reason, there is a concern that the development of the charge alignment phase is suppressed.

  The present invention has been made in view of the above problems, and an object thereof is to provide a charge orbital-aligned perovskite manganese oxide thin film obtained by a polycrystalline thin film having switching characteristics comparable to a bulk single crystal and the thin film. And a method of manufacturing the thin film.

  The inventors of the present invention have studied the effects of substrate distortion and defects on the charge orbital order, particularly focusing on the charge orbital alignment plane orientation in the thin film form, and as a result of extensive investigation, The inventors considered that it was possible to solve the influence of defects at the same time, and led to the invention of the perovskite manganese oxide thin film and the manufacturing method thereof shown below.

  In order to solve the above problems, a perovskite manganese oxide thin film according to the present invention is a perovskite manganese oxide thin film showing charge alignment and electron orbit alignment formed on a substrate, wherein the crystal lattice is the surface of the substrate. The charge trajectory alignment surface, which is oriented in a direction parallel to the surface of the substrate and in which charges are aligned and the order of 3d electron trajectories, is also non-parallel to the substrate surface. .

  According to the above configuration, charge orbital order and lattice deformation accompanying switching thereof easily occur in both the in-plane direction and the film thickness direction, and it becomes possible to realize anisotropic lattice deformation with respect to the charge orbital alignment plane. . Furthermore, since it is possible to grow a large domain of the charge orbital alignment phase not only in the film thickness direction but also in the in-plane direction of the thin film, it has many switching characteristics comparable to a bulk single crystal that is less affected by substrate distortion and defects. Obtained with a crystalline thin film.

  In order to solve the above-described problems, a switching element of the present invention includes the perovskite manganese oxide thin film.

  Therefore, according to said structure, the switching characteristic comparable to the switching element using the bulk single crystal with little influence of a board | substrate distortion and a defect can be acquired.

  A method for producing a perovskite manganese oxide thin film according to the present invention is a method for producing a perovskite manganese oxide thin film that is formed on a substrate and exhibits charge alignment and electron orbital alignment, in order to solve the above-described problems, The perovskite manganese oxide thin film has a charge orbit alignment surface, which is a surface in which the crystal lattice is oriented in a direction parallel to the substrate surface, and the charges are aligned and the orbits of 3d electrons are also ordered. It is characterized by being formed so as to be non-parallel to the surface.

  According to the above manufacturing method, a polycrystalline thin film having switching characteristics comparable to a bulk single crystal with little influence of substrate distortion and defects can be obtained.

  As described above, in the perovskite manganese oxide thin film according to the present invention, the crystal lattice is oriented in a direction parallel to the substrate surface, and the charge orbit alignment surface is not parallel to the substrate surface. is there.

  Therefore, charge orbital order and lattice deformation associated with switching thereof easily occur in both the in-film direction and the film thickness direction, and anisotropic lattice deformation can be realized with respect to the charge orbit alignment plane. Furthermore, since it is possible to grow a large domain of the charge orbital alignment phase not only in the film thickness direction but also in the in-plane direction of the thin film, it has many switching characteristics comparable to a bulk single crystal that is less affected by substrate distortion and defects. Obtained with a crystalline thin film.

  The perovskite manganese oxide thin film may be formed on the buffer film or the electrode film formed on the substrate.

  Therefore, the perovskite manganese oxide thin film of the present invention can be produced on a glass substrate, a silicon substrate, a compound semiconductor substrate or the like via a buffer film or an electrode film. Therefore, the perovskite manganese oxide thin film of the present invention can be easily applied to actual devices. Further, even when the perovskite manganese oxide thin film of the present invention is formed on the buffer film or the electrode film as described above, the same effect as that of the direct formation on the substrate can be obtained. That is, even when formed on a buffer film or an electrode film, a switching characteristic comparable to that of a single crystal bulk can be obtained by using a polycrystalline film that can be easily manufactured.

  In the perovskite manganese oxide thin film of the present invention, the charge orbit alignment surface may be substantially perpendicular to the substrate surface.

  In this case, a single-domain charge-orbital ordered phase with a uniform domain direction can be realized. For this reason, there is an effect that the charge orbital alignment phase can be uniformly formed over the entire film. Further, by adopting a configuration in which signals are input and output in a direction perpendicular to the charge trajectory alignment plane, there is an effect that a change in resistance value can be further increased.

  The perovskite manganese oxide thin film of the present invention is formed on the surface of the substrate or the buffer film or electrode film formed on the substrate having a crystal orientation of (110) or a surface substantially equivalent thereto. May be.

  Here, the crystal orientation is a cubic or tetragonal crystal orientation. Further, examples of the plane substantially equivalent to the (110) plane include (101) plane and (011) plane in cubic crystals.

  According to the above configuration, a perovskite manganese oxide thin film in which the crystal lattice is oriented in a direction parallel to the substrate surface and the charge orbit alignment surface is substantially perpendicular to the substrate surface can be easily obtained. Can be formed.

  The switching element of the present invention comprises any of the perovskite manganese oxide thin films described above.

  Therefore, switching characteristics comparable to those of a switching element using a bulk single crystal that is less affected by substrate distortion and defects can be obtained.

  The method for producing a perovskite manganese oxide thin film according to the present invention includes a perovskite manganese oxide thin film in which the crystal lattice is oriented in a direction parallel to the substrate surface, and the charge orbit alignment surface is non-parallel to the substrate surface. It forms so that it becomes.

  According to the above method, a polycrystalline thin film having switching characteristics comparable to a bulk single crystal with little influence of substrate distortion and defects can be obtained.

  Note that a buffer film or an electrode film may be formed on the substrate, and the perovskite manganese oxide thin film may be formed on the buffer film or the electrode film.

  Therefore, the perovskite manganese oxide thin film can be easily applied to actual devices. In addition, switching characteristics comparable to a single crystal bulk can be obtained by using a polycrystalline film that can be easily manufactured.

  The perovskite manganese oxide thin film may be formed on the surface of the substrate or a buffer film or an electrode film formed on the substrate having a crystal orientation of (110) or a surface substantially equivalent thereto.

  In this case, it is possible to easily form a perovskite manganese oxide thin film in which the crystal lattice is oriented in a direction parallel to the substrate surface and the charge orbit alignment surface is disposed substantially perpendicular to the substrate surface. .

  Further, the surface spacing of the charge trajectory alignment plane may be controlled by an in-plane lattice constant on the substrate or on the buffer film or electrode film formed on the substrate.

  According to the above method, for example, the substrate distortion is adjusted by adjusting the in-plane lattice constant by appropriately selecting the material of the substrate or the buffer film or electrode film formed on the substrate, and the charge trajectory alignment surface is adjusted. The surface spacing can be controlled. Thereby, since the degree of carrier hopping between the charge orbit alignment planes can be controlled, the resistance value associated with the charge orbit order can be adjusted.

〔Example〕
An embodiment of the present invention will be described below with reference to FIGS. The gist of the present invention is not limited by the present embodiment.

FIG. 2 shows an Nd _1-x Sr _x MnO ₃ film 1 (x = 0.48 to 0.51) which is a perovskite manganese oxide thin film (charge orbital aligned perovskite manganese oxide thin film) according to the present embodiment. It is sectional drawing. This Nd _1-x Sr _x MnO ₃ film 1 is an element (switching element) based on the principle of switching charge orbital alignment (a state where 3d electron orbital is ordered together with charge alignment) using an external field, For example, the present invention is applied to a nonvolatile memory element that switches charge orbit alignment using a magnetic field, an electric field, light, or the like, or an optical element that utilizes polarization change.

As shown in FIG. 2, the Nd _1-x Sr _x MnO ₃ film 1 has a film thickness on a SrTiO ₃ single crystal substrate (SrTiO ₃ (110) single crystal substrate) 2 having a plane orientation (crystal orientation) of (110). It is formed at 80 nm. The crystal system of SrTiO ₃ is cubic and the lattice constant is 3.905９０.

The Nd _1-x Sr _x MnO ₃ film 1 was manufactured under the following conditions using a laser ablation method. As the target, a polycrystalline material produced by a solid phase reaction method and formed into a 20 mmφ cylindrical shape is used, and the composition is stoichiometric.

First, the SrTiO ₃ (110) single crystal substrate 1 was mounted in a vacuum chamber and then evacuated to 1.3 × 10 ⁻⁶ Pa (1 × 10 ⁻⁸ Torr) or less. Thereafter, 0.13 Pa (1 mTorr) of high purity oxygen gas was introduced. Then, the SrTiO ₃ (110) single crystal substrate was heated to 830 ° C., and carbon and hydrate adsorbed on the surface were removed.

Next, the substrate temperature was set to 830 to 840 ° C., which is the substrate temperature at the time of manufacturing the thin film (Nd _1-x Sr _x MnO ₃ film 1). The oxygen pressure was 0.13 Pa (1 mTorr).

Next, the target was irradiated with a KrF excimer laser having a wavelength of 248 nm at a power of 100 mJ at the laser beam introduction port of the chamber, thereby forming an Nd _1-x Sr _x MnO ₃ film 1 having a thickness of 80 nm.

  Thereafter, oxygen gas at 1 atm was introduced into the chamber, annealed at 500 ° C. for 60 minutes, and then cooled to room temperature over 40 minutes. Note that the surface of the high-speed reflected electron diffraction image after deposition of the thin film is flat because a streak pattern is observed.

In order to investigate the structure and characteristics of the Nd _1-x Sr _1-x MnO ₃ film 1 formed as described above, the following experiment was performed. In the following, experimental results are mainly shown for x = 0.5, that is, the Nd _0.5 Sr _0.5 MnO ₃ film 1.

FIG. 3 shows a profile obtained by X-ray diffraction (2θ-θ diffraction) performed for examining the structure of the Nd _0.5 Sr _0.5 MnO ₃ film 1. Two peaks α and β having strong intensities are from the substrate, and peaks α ′ and β ′ from the thin film are observed on the right side (high angle side) of each peak α and β. These are diffraction peaks from the low angle side to the high angle side in this figure, where α ′ is the (110) plane and β ′ is the (220) plane.

From this result, it can be seen that the Nd _0.5 Sr _0.5 MnO ₃ film 1 is oriented in a direction perpendicular to the substrate. The lattice constant in the direction perpendicular to the substrate surface ([110] axis) was 5.38 mm.

Furthermore, in order to investigate the lattice constant in the in-plane direction, reciprocal lattice mapping measurement was performed on the (310) peak. The result is shown in FIG. The horizontal axis in FIG. 4 represents a value that is inversely proportional to the lattice constant in the [−110] axis direction in the substrate in-plane direction, and the vertical axis is a value that is inversely proportional to the lattice constant in the direction perpendicular to the substrate ([110] direction). Represents. As a result of the reciprocal lattice mapping measurement, the lattice constant of the [−110] axis in the Nd _0.5 Sr _0.5 MnO ₃ film 1 was 5.45 異 な り unlike the in-plane lattice constant (5.52 Å) of the substrate.

Next, in order to examine another axis in the in-plane direction, that is, the lattice constant in the [001] direction, a reciprocal lattice mapping measurement on the (222) peak was performed. The result is shown in FIG. The horizontal axis of FIG. 5 represents a value inversely proportional to the lattice constant in the [001] axis direction which is the in-plane direction, and the vertical axis represents a value inversely proportional to the lattice constant in the direction perpendicular to the substrate ([110] direction). ing. As a result of the reciprocal lattice mapping measurement, the lattice constant in the [001] axis direction of the Nd _0.5 Sr _0.5 MnO ₃ film 1 is slightly different from the in-plane lattice constant (3.905 Å) of the substrate, and is 3.89 Å. there were. Note that two diffraction peaks are observed in the (110) direction, which is considered to be due to the rotation and distortion of the Mn—O octahedron.

The above results are summarized in FIG. FIG. 6 is an explanatory diagram for comparing the lattice constant in the SrTiO ₃ (110) substrate 2 and the lattice constant in the Nd _0.5 Sr _0.5 MnO ₃ film 1. The cubes indicated by thin lines in the figure indicate the lattice of the SrTiO ₃ (110) substrate 2, and the thick line is the lattice constant of the Nd _0.5 Sr _0.5 MnO ₃ film 1 obtained by X-ray diffraction. .

As shown in this figure, the lattice constant of the Nd _0.5 Sr _0.5 MnO ₃ film 1 in the direction perpendicular to the substrate surface ([110] direction) is the lattice constant of the SrTiO ₃ substrate 2 (√2 · a _sub = 5.52 ａ, a _sub represents a mismatch of −2.5% compared to the lattice constant in the <100> direction of the SrTiO ₃ substrate = 3.905）). The lattice constant of the Nd _0.5 Sr _0.5 MnO ₃ film 1 with respect to the two axes in the substrate plane is −1.3% in the [−110] axis direction and −0 in the [001] axis direction. Each has a 5% mismatch. That is, the Nd _0.5 Sr _0.5 MnO ₃ film 1 is an orthorhombic crystal having different triaxial lengths and orthogonal to each other.

Here, the [−110] axis is the a-axis, the [110] axis is the b-axis, and the [001] axis is the c-axis. It can be compared with the lattice constant. Note that the lattice constants of the single crystal at room temperature are a = 5.48 Å, b = 5.43 Å, and c / 2 = 3.82 Å. On the other hand, the lattice constants of the Nd _0.5 Sr _0.5 MnO ₃ film 1 are a = 5.45Å, b = 5.38Å, and c / 2 = 3.89Å. That is, the Nd _1-x Sr _x MnO ₃ film 1 is completely relaxed in the [−110] axial direction (a-axis direction) in the substrate plane (the lattice change is not affected by the substrate distortion). It can be seen that the substrate extends in the [001] axial direction (c-axis direction) due to substrate distortion.

FIG. 1 is an explanatory view showing the arrangement of orthorhombic crystal axes and charge orbital alignment in the Nd _0.5 Sr _0.5 MnO ₃ film 1. In the figure, black circles represent Mn ³⁺ ions, white circles represent Mn ⁴⁺ ions, and a state in which orbits composed of 3x ² -r ² and 3y ² -r ² are alternately arranged is shown. The charge orbital alignment plane composed of the Mn—O plane is a (00l) plane, and the Nd _0.5 Sr _0.5 MnO ₃ film 1 is arranged perpendicular to the substrate plane and is stacked in the c-axis direction. ing.

  In addition, the lattice constants in the two-axis (a-axis and b-axis) directions on the charge orbit alignment plane [(001) plane] are a = 5.45Å and b = 5.38Å, which is anisotropic as in the case of the single crystal. It has become.

On the other hand, the difference from the single crystal is that the c-axis length, that is, the charge orbit alignment plane interval is long. This is considered to be due to an extension strain acting in the c-axis direction. Thus, for example, instead of the SrTiO ₃ substrate 2, by using a substrate having a lattice constant different from the SrTiO ₃ substrate 2 by the substrate strain that acts on the c-axis direction is changed, to adjust the charge orbital ordering spacing It becomes possible. This is presumably because the degree of carrier hopping between the charge orbit alignment planes changes by adjusting the substrate distortion.

In this way, by adjusting (controlling) the charge orbit alignment plane spacing, it is possible to adjust the resistance value associated with the charge orbit order. As the substrate in place of SrTiO ₃ substrate 2, for example, a cubic substrate lattice constant _{3.87Å (LaAlO 3) 0.3 - (} SrAl 0.5 Ta 0.5 O 3) 0.7 (LSAT Or LaAlO ₃ which is a pseudo cubic substrate having a lattice constant of 3.87Å can be used.

FIG. 7 is a graph showing the temperature dependence of the magnetization of the Nd _0.5 Sr _0.5 MnO ₃ film 1. The vertical axis in this graph represents the magnetization M normalized in units of Bohr magnetons per Mn, and the horizontal axis represents temperature. The white circles (ZFC) in the figure indicate the results of measurement while raising the temperature to 300 K after applying a magnetic field of 0.5 T (= 5000 Oe) after cooling to 5 K in a zero magnetic field. Further, the black circle (FC) shows the result when the measurement was continued while cooling again from 300K to 5K in a magnetic field.

  As shown in this figure, it was observed together with hysteresis that ferromagnetism was developed at 250K or less, and that ferromagnetic ferromagnetism-antiferromagnetic transition accompanying the development of the charge orbit alignment phase was developed at 160K or less.

FIG. 8 is a graph showing the temperature dependence of the resistivity in the Nd _0.5 Sr _0.5 MnO ₃ film 1. The vertical axis represents the logarithm of the resistivity (Resistivity), and the horizontal axis represents the temperature (Temperature). Resistance measurement is performed using a standard four-terminal method, and an alloy of gold and palladium is formed on the electrode by sputtering. The measurement current was 10 μA. The magnetic field H and current i were applied along the [001] axis. Moreover, the thick line in a figure is the result measured while falling from 300K to 5K, and the thin line represents the result measured while raising the temperature from 5K to 300K. In the figure, the data indicated as ZFC (zero field cool) is the result of measurement in a zero magnetic field, and the data indicated as 0.5T, 1T, 2T, 3T, 4T, and 5T are on the [001] axis. It is a measurement result at the time of changing the magnetic field applied along with each value.

As shown in this figure, the Nd _0.5 Sr _0.5 MnO ₃ film 1 shows a metallic behavior at 220 K or less, and an increase in resistance accompanying the development of the charge orbital alignment phase is obtained with hysteresis at 160 K or less. Yes.

  Further, as the magnetic field is increased to 0.5T and 1T to 5T, the resistance decreases by two orders of magnitude or more according to the magnetic field (magnetic resistance). That is, the charge orbital alignment phase can be switched to metal by a magnetic field.

These results indicate that the charge trajectory alignment plane and the switching thereof are facilitated by arranging the charge trajectory alignment plane in a direction perpendicular to the substrate surface, thereby facilitating lattice deformation in the charge trajectory alignment plane. It shows a characteristic that is superior to the results of conventional thin films. This result also shows that the charge orbit alignment order sensitive to a random field is expressed and switched in the Nd _0.5 Sr _0.5 MnO ₃ film 1 and is a defect that cannot be avoided in the polycrystalline film. It shows that the amount can be reduced to a degree sufficient to utilize switching.

When compared with a single crystal, the magnetization shows 1.5 μ _B / Mn, which is about half (3 μ _B / Mn for a single crystal), and the resistance value in the ground state (5 K) in a zero magnetic field is 10 ^−1. Ωcm, which is about three orders of magnitude lower (10 ² Ωcm for a single crystal). That is, in the single crystal, the magnetic field required for complete metallization is 7T, but in the Nd _0.5 Sr _0.5 MnO ₃ film 1, the magnetic field is lowered to 5T.

  This is because the random field caused by the defects introduced in the polycrystalline film disturbs the ferromagnetic phase and the charge orbit alignment phase, and also increases the c-axis length, that is, the charge orbit alignment plane spacing. This is considered to be an important factor. This is because the elongation of the c-axis length (elongation of charge orbit alignment plane spacing) suppresses ferromagnetism in the ferromagnetic metal phase, and the degree of freedom that the in-plane orbit in the charge orbit alignment phase faces in the inter-plane direction. This is because the resistance value is reduced because the carrier hopping between the surfaces is promoted.

  Therefore, by adjusting the substrate strain in one direction in the substrate surface along the c-axis length, the surface spacing of the charge orbit alignment arranged perpendicular to the substrate surface can be controlled, and the charge orbit alignment phase in the charge orbit alignment phase can be controlled. It becomes possible to control the resistance value.

Further, in the Nd _0.5 Sr _0.5 MnO ₃ film 1, the charge orbit alignment plane is arranged perpendicular to the substrate, and the crystal axes in the plane are perfectly oriented. Even if the grain boundary is included, domains aligned in one direction are formed. This provides uniform properties across the entire film compared to the multi-domain state. For example, in the case of a device integrated on a wafer, it is possible to suppress variations in characteristics from device to device.

FIG. 9 shows the temperature dependence of the resistivity in the Nd _0.5 Sr _0.5 MnO ₃ film 1 when a magnetic field and current are applied along the [1-10] axis (parallel to the [−110] axis). It is a graph which shows. The vertical axis represents the logarithm of resistivity, and the horizontal axis represents temperature. For comparison, the result (white circle in the figure) in a zero magnetic field in which a magnetic field and a current are applied along the [001] axis is also shown. Resistivity measured perpendicular to the [001] axis or charge trajectory alignment plane (when applying a magnetic field and current along the [001] axis) was measured parallel to the [1-10] axis or charge trajectory alignment plane. It can be seen that it is about an order of magnitude higher than the resistivity (when a magnetic field and current are applied along the [1-10] axis). This anisotropy is obtained by aligning the charge orbitals, especially the orbital alignment planes, and as described above, a single domain or a domain with a uniform orientation is formed even though it contains defects due to the polycrystalline film. It is shown that it is done.

  This anisotropy is, for example, when used as a memory element or a transistor that uses a resistance value, by setting a signal to be input / output in the c-axis direction, that is, perpendicular to the charge trajectory alignment plane, It shows that it is possible to take a larger change.

By the way, Nd _1-x Sr _x MnO ₃ has almost no difference in average lattice constant when the hole doping concentration is in the range of x = 0.48 to 0.51, but when x = 0.48, the ferromagnetic metal phase, x = 0.49, the charge orbital alignment phase coexisting with the ferromagnetic metal phase, x = 0.50, the charge orbital alignment phase, and x = 0.51, the layered antiferromagnetic metal phase may coexist in the layered antiferromagnetic metal phase. Single crystals have been reported.

Therefore, when the value of x in the Nd _1-x Sr _x MnO ₃ film is changed in order to investigate the case where the charge orbital alignment phase coexists with various phases such as a ferromagnetic metal phase and a layered antiferromagnetic metal phase. The magnetic properties were measured.

FIG. 10 is a graph showing magnetic characteristics when the value of x in the Nd _1-x Sr _x MnO ₃ film 1 is changed to 0.48, 0.49, 0.50, 0.51. That is, the Nd _1-x Sr _x MnO ₃ film 1 (x = 0.48,0.49,0.50,0.51) produced on the SrTiO ₃ (110) single crystal substrate 2 by the production method described above. It is a graph which shows a magnetic characteristic. In this graph, the vertical axis represents the magnetization M normalized in units of Bohr magnetons per Mn, and the horizontal axis represents the temperature. The thin line in the figure shows the result of measurement while raising the temperature to 300 K after applying a magnetic field of 0.5 T (= 5000 Oe) after cooling to 5 K in a zero magnetic field. In addition, the thick line in the figure shows the result of measurement while cooling again from 300K to 5K in a magnetic field.

As shown in this figure, the polycrystalline thin film (Nd _1-x Sr _x MnO ₃ film 1) also has a result comparable to the characteristics known for single crystals, and thus there are various charge-orbit alignment phases. It is apparent that the above-described effects (effects obtained in the Nd _0.5 Sr _0.5 MnO ₃ film 1) can be obtained even when coexisting with a small phase.

[Comparative example]
The Nd _1-x Sr _x MnO ₃ film 1 according to the present embodiment is formed on the SrTiO ₃ (110) single crystal substrate 2 having the (110) plane orientation, but for comparison with this, the plane orientation is A Nd _0.5 Sr _0.5 MnO ₃ film (not shown) having a film thickness of 190 nm is formed on a (100) SrTiO ₃ single crystal substrate (SrTiO ₃ (100) single crystal substrate), and its structure and characteristics Investigated about.

The average lattice constant determined as the cube root of the unit cell volume (58.11 Å) at room temperature of the Nd _0.5 Sr _0.5 MnO ₃ single crystal is 3.844 、, and the SrTiO ₃ (100) single crystal and The lattice mismatch is about 1.6%, and tensile strain acts.

The manufacturing method of the Nd _0.5 Sr _0.5 MnO ₃ film was the same as the conditions shown in the examples.

  In addition, when the state at the time of thin film manufacture was observed by the high-speed reflection electron beam diffraction, the intensity vibration of the specular spot (spot by specular reflection from the substrate or the outermost surface of the thin film) was observed. This vibration period suggests the possibility of corresponding to two-dimensional growth in the layer-by-layer mode for each perovskite unit cell. Therefore, it can be said that the manufacturing conditions are preferable.

In addition, a Laue diffraction spot and a streak pattern were observed in the high-speed reflected electron diffraction image after the thin film (Nd _0.5 Sr _0.5 MnO ₃ film) was deposited. Therefore, the surface of this Nd _0.5 Sr _0.5 MnO ₃ film is flat at the atomic layer level.

  The results of examining the comparative thin film thus prepared are shown in FIGS.

FIG. 11 shows a profile obtained by X-ray diffraction (2θ-θ diffraction) performed to examine the structure of the thin film (Nd _0.5 Sr _0.5 MnO ₃ film) in the comparative example.

  Three strong peaks a, b and c are from the substrate, and peaks a ', b' and c 'observed on the right side (high angle side) of each peak are from the thin film. These are diffraction peaks from the low angle side to the high angle side in this figure, where a ′ is the (001) plane, b ′ is the (002) plane, and c ′ is the (003) plane.

  From this result, it can be seen that the thin film in the comparative example is (00 l) oriented in the direction perpendicular to the substrate. The lattice constant in the direction (c-axis) perpendicular to the substrate surface was 3.79 mm.

  Furthermore, FIG. 3 shows the result of reciprocal lattice mapping measurement on the (114) peak, which was performed to examine the lattice constant in the in-plane direction. The horizontal axis in FIG. 12 represents a value inversely proportional to the lattice constant in the in-plane direction, and the vertical axis represents a value inversely proportional to the lattice constant in the direction perpendicular to the substrate (c-axis). As a result of reciprocal lattice mapping measurement, the in-plane lattice constant (lattice constant in the in-plane direction) of the thin film in the comparative example is slightly different from the in-plane lattice constant of the substrate in the two in-plane (a-axis and b-axis) directions. 3.89 cm. That is, the lattice arrangement is such that two axes in the plane are isotropically extended and one axis in the film thickness direction is contracted, and the substrate distortion cannot be completely relaxed (the lattice change is affected by the substrate distortion). I understand).

As a result, the Nd _0.5 Sr _0.5 MnO ₃ film 1 is completely relaxed in the [−110] axial direction (a-axis direction) in the substrate plane (the lattice change is not affected by the substrate strain). The [001] axial direction (c-axis direction) is greatly different from the case of extending due to substrate distortion (see FIGS. 3 to 6). In the comparative example, the charge orbital alignment phase exists in the Mn—O plane extending in two axes. Therefore, when the charge orbital alignment surface appears, it is considered that the charge orbit alignment phase exists in parallel to the substrate surface.

  FIG. 13 is a graph showing the temperature dependence of the magnetization of the thin film (the alignment film) in the comparative example in which the substrate distortion is partially relaxed in this way. In this graph, the vertical axis represents the magnetization M normalized in units of Bohr magnetons per Mn, and the horizontal axis represents the temperature. Further, the thin line (ZFC) in the figure shows the result of measurement while cooling to 5K in a zero magnetic field, applying a 1T (= 10000 Oe) magnetic field, and then raising the temperature to 300K. In addition, the thick line (FC) in the figure shows the result of measurement while cooling again from 300K to 5K in a magnetic field.

As described above, the Nd _0.5 Sr _0.5 MnO ₃ film 1 exhibits ferromagnetism at 250 K or lower and charge orbit alignment at 160 K or lower, as reported in the bulk (bulk single crystal). A ferromagnetic ferromagnetism-antiferromagnetic transition accompanying the development of the phase appears (see FIG. 7).

  On the other hand, as shown in FIG. 13, in the thin film of the comparative example, the development of ferromagnetism at 250 K or less is not confirmed. Therefore, the ferromagnetic-antiferromagnetic transition accompanying the development of the charge orbital alignment phase at 160 K is not observed, and exhibits antiferromagnetic behavior within the measurement temperature range.

  FIG. 14 is a graph showing the temperature dependence of resistivity in the thin film of the comparative example. Resistance was performed using a standard four-terminal method. The measurement current was 10 μA.

The vertical axis in FIG. 14 represents the logarithm of resistivity, and the horizontal axis represents temperature. As shown in this figure, the thin film of the comparative example increases in resistance with decreasing temperature in a zero magnetic field, and exhibits a semiconductor behavior (see ZFC in the figure). That is, since the thin film of the comparative example does not relax the substrate strain, it can be seen that the magnetic properties and the transport properties are modulated by the extension strain. That is, as described in the section of “Background Art”, since this extension strain acts to stabilize the charge orbital alignment phase, the phase transition to the ferromagnetic phase is suppressed, and the resistance increases at a low temperature. In addition, under a magnetic field of 3T and 5T, the resistivity decreases to about 10 ⁻² Ωcm, and exhibits a metallic behavior with little temperature dependence within the measurement temperature range. The temperature dependence of the resistivity is very similar to the behavior in the layered antiferromagnetic metal phase, which is the overdoping phase of Nd _0.5 Sr _0.5 MnO ₃ . Therefore, the decrease in resistivity (magnetoresistance) under the magnetic field of 3T and 5T is considered to be a transition from the charge-orbit alignment insulating phase to the layered antiferromagnetic metal phase.

This result shows that, in the Nd _0.5 Sr _0.5 MnO ₃ film 1, for example, in a zero magnetic field, it shows a metallic behavior at 220K or less, and at 160K or less, the resistance increases due to the appearance of the charge orbital alignment phase. Is significantly different from that obtained (see FIG. 8). That is, in the Nd _0.5 Sr _0.5 MnO ₃ film 1, the charge orbit alignment plane is arranged in the direction perpendicular to the substrate surface, whereby lattice deformation in the charge orbit alignment plane is facilitated, and charge orbit alignment transition and Although the switching becomes easy, it is shown that such an effect cannot be obtained with the thin film in the comparative example.

Thus, the Nd _0.5 Sr _0.5 MnO ₃ film of the comparative example manufactured on the SrTiO ₃ (100) single crystal substrate is considered to have a charge orbital alignment plane parallel to the substrate surface. _{In the 0.5} Sr _0.5 MnO ₃ film, switching characteristics such as single crystal or Nd _0.5 Sr _0.5 MnO ₃ film 1 cannot be obtained. The main reason is considered to be due to substrate distortion as described above.

That is, as shown in the comparative example, in the Nd _0.5 Sr _0.5 MnO ₃ film manufactured on the SrTiO ₃ (100) single crystal substrate and having the charge orbit alignment surface parallel to the substrate surface, The track alignment surface is isotropically affected by substrate distortion. As a result, the lattice deformation of the charge trajectory alignment surface is considered to be isotropic.

On the other hand, it is considered that lattice deformation in the film thickness direction is easier than in-plane lattices that are directly affected by the substrate. Therefore, as in the case of the Nd _1-x Sr _x MnO ₃ film 1 according to the present embodiment, if the charge trajectory alignment plane is not parallel to the substrate surface (if it is not parallel), the lattice change in the charge trajectory alignment plane Can be easily deformed in at least one direction. As a result, lattice deformation during switching can be facilitated.

  As described above, in the perovskite manganese oxide thin film of the present invention, the lattice (crystal lattice) is oriented in a direction parallel to the substrate surface, and the charge orbit alignment surface is not parallel to the substrate surface (non- Parallel). For this reason, lattice deformation accompanying switching of the charge orbital order easily appears in both the in-plane direction and the film thickness direction of the thin film. This enables anisotropic lattice deformation with respect to the charge trajectory alignment surface.

  In the perovskite manganese oxide thin film of the present invention, a domain having a large charge orbital alignment phase can be grown not only in the film thickness direction but also in the thin film in-plane direction. For this reason, switching characteristics comparable to a bulk single crystal with little influence of substrate distortion and defects can be obtained with a polycrystalline thin film.

  Furthermore, in the perovskite manganese oxide thin film of the present invention, the inter-plane lattice constant of the substrate can be used to control the spacing between the charge orbit alignment planes and to adjust the resistance value associated with the charge orbital order. That is, the substrate distortion can be adjusted by changing the in-plane lattice constant of the substrate, the surface spacing of the charge trajectory alignment surfaces can be controlled, and the degree of carrier hopping between the charge trajectory alignment surfaces can be controlled. The resistance value associated with orbital order can be adjusted.

The in-plane lattice constant of the substrate can be adjusted, for example, by changing the material of the substrate. That is, in the present embodiment, a perovskite single crystal substrate (SrTiO ₃ (110) single crystal substrate 2) is used, but instead, for example, a cubic substrate having a lattice constant of 3.87３ (LaAlO ₃ ) _{0 .3—} (SrAl _0.5 Ta _0.5 O ₃ ) _0.7 (referred to as LSAT), LaAlO ₃ which is a pseudo-cubic substrate having a lattice constant of 3.87Å, or the like may be used. That is, a substrate having an in-plane lattice constant such that the perovskite manganese oxide thin film has a desired resistance value may be selected.

  In the perovskite manganese oxide thin film of the present invention, the charge orbit alignment plane is substantially perpendicular to the substrate surface. In this case, a single-domain charge orbital ordered phase with aligned domain directions can be realized, so that the charge orbital aligned phase can be uniformly formed over the entire thin film. Therefore, a larger resistance change can be realized by inputting and outputting signals in the direction between the charge trajectory alignment planes.

  The perovskite manganese oxide thin film according to the present embodiment may be oriented in a direction perpendicular to the substrate surface as long as the crystal lattice is oriented in a direction parallel to the substrate surface. Further, the perovskite manganese oxide thin film according to the present embodiment is different from the (101) orientation film in Non-Patent Document 3 described above in that the crystal lattice is oriented in a direction parallel to the substrate surface. That is, the (101) orientation film in Non-Patent Document 3 is oriented in a direction perpendicular to the substrate surface, but cannot be oriented because a domain enters in a direction parallel to the film surface (in-plane direction of the substrate).

In this embodiment, the perovskite single crystal substrate (SrTiO ₃ (110) single crystal substrate 2) is used for the sake of simplicity, but the present invention is not limited to this. For example, as described above, instead of the SrTiO ₃ (110) single crystal substrate 2, (LaAlO ₃ ) _0.3 — (SrAl _0.5 Ta _0.5 O ₃ ) which is a cubic substrate having a lattice constant of 3.87Å. ) _0.7 (referred to as LSAT) or LaAlO ₃ which is a pseudo cubic substrate having a lattice constant of 3.87Å may be used. Alternatively, other oxide substrates may be used.

In addition, a buffer film or an electrode film of Pt, Ir, IrO ₂ , RuO ₂ , SrRuO ₃ or the like is formed on a substrate such as a glass substrate, a silicon substrate, or a compound semiconductor substrate according to the present invention, and perovskite manganese oxide The physical thin film may be formed on the substrate via a buffer film or an electrode film. In an actual device, since there are few opportunities to use a perovskite single crystal substrate, it is desirable to manufacture it on a substrate such as a glass substrate, a silicon substrate, or a compound semiconductor substrate via a buffer film or an electrode film. That is, in an actual device, it is practical to manufacture on a glass substrate, a silicon substrate, a compound semiconductor substrate, etc. via a buffer film or an electrode film. Even when the perovskite manganese oxide thin film of the present invention is formed on the buffer film or the electrode film as described above, the perovskite manganese oxide thin film has substantially the same effect as that formed directly on the perovskite single crystal substrate. That is, even when formed on a buffer film or an electrode film, a switching characteristic comparable to that of a single crystal bulk can be obtained by using a polycrystalline film that can be easily manufactured.

  Further, in this case, the resistance value of the perovskite manganese oxide thin film can be set to a desired value by adjusting the in-plane lattice constant of the buffer film or the electrode film as in the case of forming the perovskite manganese oxide thin film on the perovskite single crystal substrate. Can be controlled to a value.

  Further, the perovskite manganese oxide thin film of the present invention is a surface represented by (110) using a cubic or tetragonal crystal orientation on a substrate or a buffer film or an electrode film formed on the substrate, Or it is preferable to form in the surface substantially equivalent to this. As a result, it is possible to easily form a perovskite manganese oxide thin film in which the crystal lattice is oriented in a direction parallel to the substrate surface and the charge orbit alignment surface is substantially perpendicular to the substrate surface. Note that examples of the plane substantially equivalent to the (110) plane include a (101) plane and a (011) plane in a cubic crystal.

Further, as the perovskite manganese oxide thin film (charge orbital alignment perovskite manganese oxide thin film), here, an Nd _1-x Sr _x MnO ₃ film (x = 0.48 to 0.51) sensitive to strain and defects was used. However, it is not limited to this. The present invention is, for example, other charge orbital order perovskite manganese oxide thin film, _Bi 0.5 _Sr 0.5 MnO ₃ and YBaMn ₂ O _6, particularly showing the charge orbital ordering above room _{temperature, HoBaMn 2 O 6, DyBaMn 2} O ₆ , TbBaMn ₂ O ₆ , etc.

Further, in the present embodiment, by forming the _{Nd 1-x} Sr _x MnO ₃ layer 1 on SrTiO ₃ (110) single crystal substrate 2 of plane orientation _{(110), Nd 1-x} Sr x MnO 3 Although the charge orbit alignment surface in the film 1 is substantially perpendicular to the substrate surface, the method for producing the charge orbit alignment perovskite manganese oxide thin film of the present invention is not limited to this. That is, any method can be used as long as the crystal lattice is oriented in a direction parallel to the substrate surface and the charge orbit alignment surface is non-parallel to the substrate surface.

  Further, as described above, the perovskite manganese oxide thin film of the present invention can be applied to an element (switching element) based on the principle of switching charge orbit alignment using an external field such as a nonvolatile memory element or an optical element. By applying the perovskite manganese oxide thin film of the present invention to these switching elements, switching characteristics comparable to those using a bulk single crystal with little influence of substrate distortion and defects can be obtained.

  In addition, the present invention relates to a charge orbital alignment perovskite manganese that shows a charge orbital order, which is a principle of a giant resistance change applicable to a memory device, etc. It can also be expressed that the object is to provide an oxide thin film, a manufacturing method thereof, and a switching element including the thin film.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims. That is, embodiments obtained by combining technical means appropriately modified within the scope of the claims are also included in the technical scope of the present invention.

  The perovskite manganese oxide thin film of the present invention is an element based on the principle of switching charge orbit alignment using an external field, for example, a nonvolatile memory element that switches charge orbit alignment using a magnetic field, electric field, or light, or polarization. It can be applied to an optical element using change.

Charge orbit alignment in a perovskite manganese oxide thin film according to an embodiment of the present invention, that is, a perovskite manganese oxide thin film (Nd _0.5 Sr _0.5 MnO ₃ thin film) manufactured on a SrTiO ₃ (110) substrate It is explanatory drawing which shows a state. It is sectional drawing which shows the structure of the perovskite manganese oxide which concerns on one embodiment of this invention. It is a graph which shows the result of the X-ray diffraction in the perovskite manganese oxide thin film which concerns on one embodiment of this invention. It is a reciprocal lattice mapping measurement figure about a (310) peak in the perovskite manganese oxide thin film concerning one embodiment of the present invention. It is a reciprocal lattice mapping measurement figure regarding the (222) peak in the perovskite manganese oxide thin film which concerns on one embodiment of this invention. A perovskite manganese oxide thin film according to an embodiment of the present invention, SrTiO 3 ₍₁₁₀₎ of the substrate is an explanatory diagram showing a lattice constant mismatch. It is a graph which shows the temperature dependence of magnetization in the perovskite manganese oxide thin film which concerns on one embodiment of this invention. It is a graph which shows the temperature dependence of the resistivity in a magnetic field of the perovskite manganese oxide thin film which concerns on one embodiment of this invention. It is a graph which shows the anisotropy of the resistivity of an orbital alignment in-plane direction and an interplane direction in the perovskite manganese oxide thin film which concerns on one embodiment of this invention. In the perovskite manganese oxide thin film according to an embodiment of the present invention _{(Nd 1-x Sr x MnO} 3 layer) is a graph showing the composition dependence of the magnetic properties (x = 0.48~0.51). Perovskite manganese oxide thin film according to the comparative example, i.e., a graph showing a SrTiO ₃ (100) _Nd were produced on a substrate 0.5 _Sr 0.5 MnO ₃ X-ray diffraction results of the thin film. It is a reciprocal lattice mapping measurement figure regarding the (114) peak of the perovskite manganese oxide thin film which concerns on a comparative example. It is a graph which shows the temperature dependence of magnetization of the perovskite manganese oxide thin film which concerns on a comparative example. It is a graph which shows the temperature dependence of the resistivity in the magnetic field of the perovskite manganese oxide thin film which concerns on a comparative example.

Explanation of symbols

1 Nd _1-x Sr _x MnO ₃ film (perovskite manganese oxide thin film)
2 SrTiO ₃ single crystal substrate (substrate)

Claims (9)

  A perovskite manganese oxide thin film formed on a substrate exhibiting charge alignment and electron orbital alignment, wherein the crystal lattice is oriented in a direction parallel to the substrate surface, and the charge is aligned and 3d electrons A perovskite manganese oxide thin film characterized in that a charge orbital alignment surface, which is a surface in which the orbitals are ordered, is non-parallel to the substrate surface.   The perovskite manganese oxide thin film according to claim 1, wherein the perovskite manganese oxide thin film is formed on a buffer film or an electrode film formed on the substrate.   The perovskite manganese oxide thin film according to claim 1 or 2, wherein the charge orbit alignment surface is substantially perpendicular to the substrate surface.   The crystal orientation of the substrate, or a buffer film or an electrode film formed on the substrate, is formed on a (110) plane or a plane substantially equivalent thereto. The perovskite manganese oxide thin film according to any one of the above.   A switching element comprising the perovskite manganese oxide thin film according to claim 1.   A method for producing a perovskite manganese oxide thin film having a charge alignment and an electron orbital alignment formed on a substrate, wherein the perovskite manganese oxide thin film has a crystal lattice oriented in a direction parallel to the substrate surface, In addition, the perovskite manganese oxide thin film is characterized in that the charge orbital alignment plane, which is a plane in which charges are aligned and 3d electron orbitals are ordered, is non-parallel to the substrate surface. Production method.   The perovskite manganese oxide thin film according to claim 6, wherein a buffer film or an electrode film is formed on the substrate, and the perovskite manganese oxide thin film is formed on the buffer film or the electrode film. Manufacturing method.   The perovskite manganese oxide thin film is formed on the surface of the substrate or a buffer film or an electrode film formed on the substrate with a crystal orientation of (110) or a surface substantially equivalent thereto. Item 8. The method for producing a perovskite manganese oxide thin film according to Item 6 or 7. 9. The surface interval of the charge orbit alignment surface is controlled by an in-plane lattice constant on the substrate or on a buffer film or an electrode film formed on the substrate. The manufacturing method of the perovskite manganese oxide thin film of description.

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