WO2012140971A1 - ペロフスカイト型マンガン酸化物薄膜 - Google Patents
ペロフスカイト型マンガン酸化物薄膜 Download PDFInfo
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- WO2012140971A1 WO2012140971A1 PCT/JP2012/055344 JP2012055344W WO2012140971A1 WO 2012140971 A1 WO2012140971 A1 WO 2012140971A1 JP 2012055344 W JP2012055344 W JP 2012055344W WO 2012140971 A1 WO2012140971 A1 WO 2012140971A1
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- thin film
- perovskite
- manganese oxide
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- 239000010409 thin film Substances 0.000 title claims abstract description 132
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 88
- 239000000758 substrate Substances 0.000 claims abstract description 169
- 239000013078 crystal Substances 0.000 claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910002367 SrTiO Inorganic materials 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 description 72
- 230000007704 transition Effects 0.000 description 29
- 239000010408 film Substances 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 230000008859 change Effects 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 230000005291 magnetic effect Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000137 annealing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 7
- 230000014509 gene expression Effects 0.000 description 7
- 238000000608 laser ablation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012212 insulator Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000000089 atomic force micrograph Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005290 antiferromagnetic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000005162 X-ray Laue diffraction Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005224 laser annealing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 rare earth cation Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000004335 scaling law Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
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- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
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Definitions
- the present invention relates to a thin film of perovskite manganese oxide. More specifically, the present invention relates to a perovskite-type manganese oxide thin film whose electrical, magnetic, or optical properties are switched in response to a stimulus such as temperature, electric field, magnetic field, or light irradiation.
- the electronic phase In the charge alignment phase and orbital alignment phase, carriers are localized, so that the electrical resistance is high, and the electronic phase is an insulator phase. Moreover, the magnetic property of this electronic phase is an antiferromagnetic phase due to double exchange interaction. In many cases, the electronic state of the charge alignment phase or the orbital alignment phase should be regarded as a semiconductor. This is because, in the charge alignment phase or the orbital alignment phase, although the carriers are localized, the electric resistance is lower than that of a so-called band insulator. However, by convention, the electronic phase of the charge alignment phase or the orbital alignment phase is expressed as an insulator phase.
- the spin is aligned and the electronic phase is a ferromagnetic phase.
- the sign of the temperature differential coefficient of resistivity is positive is expressed as a metal phase.
- the insulator phase is redefined as “the sign of the temperature differential coefficient of resistivity is negative”.
- any one of electronic phases such as a phase in which both charge alignment and orbital alignment are established (charge orbital alignment phase: charge- and orbital- ordered phase)
- charge orbital alignment phase charge- and orbital- ordered phase
- various switching phenomena are observed in a single crystal bulk material of the substance (Patent Document 1: JP-A-8-133894, Patent Document 2: JP-A-10-255481). And Japanese Patent Laid-Open No. 10-261291).
- Such switching phenomenon is a phenomenon that appears in response to a stimulus such as a temperature change across a transition point, application of a magnetic field or electric field, or light irradiation.
- a group of substances exhibiting such a high transition temperature is characterized by containing Ba (barium) as the alkaline earth Ae.
- Ba is contained as the alkaline earth Ae, and Y (yttrium), Ho (holmium), Dy (dysprosium), Tb (terbium), Gd (gadolinium), Eu (europium), Sm having a small ion radius as the rare earth Ln. It has been reported that the transition temperature exceeds room temperature when (samarium) is used.
- Patent Document 4 Japanese Patent Laid-Open No. 2005-213078 discloses that a perovskite oxide thin film is formed using a (110) plane orientation substrate. According to this disclosure, when the in-plane four-fold symmetry is broken in the (110) plane orientation substrate, shear deformation of the crystal lattice is allowed when the formed thin film is switched. That is, in the thin film formed according to Patent Document 4, the crystal lattice is oriented parallel to the substrate surface, and the charge alignment surface and the orbital alignment surface are not parallel to the substrate surface.
- Patent Document 4 discloses that a transition at a high temperature, that is, a switching phenomenon similar to that of a bulk single crystal is realized by using a (110) plane orientation substrate.
- Patent Document 5 Japanese Patent Laid-Open No. 2008-156188 discloses an example in which the perovskite-type manganese oxide subjected to the A-site ordering is thinned.
- Patent Document 5 reports that after an amorphous thin film is once deposited by a coating light irradiation method, crystallization and A-site ordering are performed by laser annealing. Specifically, it has been confirmed by electron beam diffraction that the A site is ordered in the SmBaMn 2 O 6 thin film formed on the SrTiO 3 (lattice constant 0.3905 nm) substrate of (100) plane orientation. .
- Patent Document 5 does not disclose whether the thin film subjected to A-site ordering is a single crystal, the thin film is a polycrystalline film, that is, a film having many grains having different crystal orientations on the same substrate. In this case, the A site ordering and the charge orbital order itself are hindered by lattice defects in the thin film. Therefore, in the thin film substance disclosed in Patent Document 5, there is a concern that the transition temperature is lowered, and in the severe case, the primary phase transition itself disappears.
- JP-A-8-133894 Japanese Patent Laid-Open No. 10-255481 JP-A-10-261291 Japanese Patent Laid-Open No. 2005-213078 JP 2008-156188 A
- the perovskite-type manganese oxide in order to realize high-performance switching characteristics and uniform characteristics, it is necessary to produce a single crystal thin film with few defects, as in a general semiconductor device.
- a (110) plane orientation substrate in Patent Document 4.
- the atomic layer plane is (Ln, Ba) BO—O 2 — (Ln, Ba) BO. This is because an atomic layer composed of A sites containing B atoms or rare earth elements Ln irregularly, B sites, and O atoms is formed, and two O atoms are included adjacent to the atomic layer.
- a stack of atomic layers having a repetitive structure is shown.
- A-site ordering in the (110) -oriented thin film must occur in a plane parallel to the atomic stacking plane.
- driving force driving force
- the atomic plane grows on the (210) plane oriented substrate in the direction perpendicular to the substrate surface, that is, in the [210] axial direction so that the atomic plane becomes AeO—BO 2 —LnO—BO 2 —.
- the crystal lattice is formed with the charge orbital alignment plane greatly inclined with respect to the substrate surface as described later with reference to FIGS.
- the inventors of the present application have found that such a perovskite-type manganese oxide thin film cannot be said to have a sufficient resistance change even when trying to use a resistance change caused by a switching phenomenon such as an insulator-metal transition. Noticed.
- the charge trajectory alignment surface 11 formed in a direction close to the direction in which carriers flow is a current. It becomes a route. That is, in such a direction of the charge orbit alignment surface, the resistance change caused by the insulator-metal transition is reduced, and the resistance change that can be used when the perovskite-type manganese oxide thin film is used as a device. There is a concern that the problem will be smaller.
- the present invention has been made in view of the above problems. That is, the present invention is compatible with (1) the possibility of first-order phase transition and (2) A-site ordering necessary for switching at room temperature, and (3) charge orbit alignment. Contributing to the fabrication of various devices that use perovskite-type manganese oxide thin films by providing perovskite-type manganese oxide thin films that can fully utilize the resistance change associated with the generation and disappearance of order. To do.
- the inventors of the present application have found a means for solving this problem as a result of examining the above-mentioned problem while paying attention to the relationship between the growth direction of the perovskite-type manganese oxide thin film and the atomic stacking plane.
- the problem that the charge trajectory alignment surface is formed with a large inclination from the substrate surface can be solved by appropriately controlling the direction of crystal growth.
- a perovskite-type manganese (Mn) oxide thin film comprising barium Ba and rare earth element Ln at the A site of the perovskite crystal lattice, wherein the (m10) plane orientation (19 ⁇ m ⁇ 2) is formed so as to cover at least part of the surface of the substrate having a perovskite structure, and in the direction of [100] axis of the substrate, LnO—MnO 2 —BaO—MnO 2 —LnO.
- the atomic stacking plane in the [100] axial direction is AO—BO 2 —AO.
- Ln and Mn located at the A site while growing the thin film in the [100] axial direction.
- the charge trajectory alignment surface in the insulator phase is arranged on the side parallel to the substrate surface.
- the charge trajectory alignment plane is a (100) plane, and is a plane inclined from the substrate plane by an angle smaller than 45 degrees as a boundary.
- the charge trajectory alignment plane being parallel to the substrate surface means an arrangement in which the charge trajectory alignment plane is inclined from the substrate plane by an angle smaller than 45 degrees and larger than 0 degrees.
- the charge trajectory alignment surface being perpendicular to the substrate surface means that the charge trajectory alignment surface is inclined by an angle greater than 45 degrees and less than 90 degrees from the substrate surface.
- the A site the perovskite crystal lattice indicated as ABO 3, a cube having each oxygen constituting the oxygen octahedron in the face-centered position, thinking parallelepiped more generally, located at the apex of the cube such grating Is a point.
- the angle ⁇ with respect to the (m10) plane, which is the substrate plane can be obtained by Equation 2 when the angle of the above-described charge trajectory alignment plane, that is, the (010) plane is more specifically seen.
- ⁇ arctan (1 / m) Equation 2
- the (m10) plane orientation substrate means a substrate whose substrate surface is the (m10) plane.
- the substrate surface here is a plane on which the surface of interest of the substrate generally extends. For example, if some microscopic structure is formed on the surface of interest of the substrate, the crystal plane that defines the surface as a whole substrate, not the orientation of the individual planes that define the microscopic structure Becomes the substrate surface. Further, a deviation in orientation due to an error that remains in production, such as a miscut angle, is allowed in order to determine the substrate surface.
- the (m10) plane substrate will be described by way of a specific example.
- the (m10) orientation means that the thin film surface parallel to the substrate surface, that is, the Miller index specifying the film surface is the (m10) plane.
- the (m10) plane orientation substrate is a substrate whose orientation is such that the (210) plane is the substrate surface. That is, the (100) plane is a substrate whose plane orientation is inclined about 26.6 degrees around the [001] axis (in-plane [001] axis) included in the plane.
- Equation 2 is a general formula for the (m10) plane.
- the (100) plane of the (m10) plane orientation substrate approaches closer to the thin film surface or the substrate surface.
- the thin film surface is determined by the specification of the surface index, but it may also be specified by using an angle as the off angle for the tilted substrate surface. This correspondence is again given by Equation 2.
- the upper limit of m 19 ⁇ m holds.
- This upper limit for m corresponds to the number at which the off angle (angle ⁇ ) of the (100) plane is greater than 3 degrees. This is because it has been experimentally confirmed that when the off angle is 3 degrees or less, lattice deformation necessary for the first-order phase transition is suppressed.
- ⁇ is about 3.013 degrees.
- a perovskite-type manganese oxide thin film in which the substrate is a substrate having a (210) plane orientation.
- the configuration of this aspect makes it easiest to order the A sites while growing a thin film in the [100] axial direction.
- the (m10) plane is obtained by tilting the (010) plane in a certain direction so as to satisfy Expression 1 with the in-plane [001] axis as the center, and in other words, satisfying Expression 2 ( 100) is equivalent to tilting the surface in the opposite direction.
- the in-plane [001] axial direction of the crystal lattice is not different from the situation on the (100) plane orientation substrate, while the [1-m0] axial direction orthogonal to the in-plane [001] axis is Increases the terrace width of the (100) plane as m increases. For this reason, crystal growth becomes difficult when m is excessive. Therefore, the (210) orientation with the smallest index is most preferable from the viewpoint of thin film production.
- the substrate is a SrTiO 3 (210) plane orientation substrate, and the substrate includes a step portion having a first-type orientation plane extending in an in-plane [001] axial direction, Provided is the perovskite-type manganese oxide thin film having a concavo-convex structure including a terrace portion with a (100) plane in a direction different from the first type on the surface on which the perovskite-type manganese oxide thin film is formed. Is done.
- the configuration of this aspect it becomes easy to stack the LnO—MnO 2 —BaO—MnO 2 —LnO... And the atomic plane in which the A site is ordered in the [100] axial direction on the (100) plane terrace. .
- This is a template for a thin film formed on a surface structure consisting of a step parallel to the in-plane [001] axial direction and a (100) plane terrace formed on a SrTiO 3 (210) plane orientation substrate. This is because it can be used.
- the perovskite-type manganese oxide thin film represented by the chemical formula SmBaMn 2 O 6 is provided.
- a thin film that can obtain charge orbital order around room temperature of about 380 K can be manufactured.
- the charge orbit alignment plane is formed on the side parallel to the substrate surface, which can use the resistance change associated with the switching operation of the generation and disappearance of the charge orbit alignment order at room temperature.
- An A-site ordered perovskite-type manganese oxide thin film exhibiting a transition temperature of the charge alignment phase or the orbital alignment phase above room temperature is realized.
- FIG. 2A is a side view as viewed from the in-plane [001] axis
- FIG. 2B is a side view as viewed from the in-plane [1-20] axis.
- FIG. 3A is a cross-sectional view of a plane containing atoms of A sites and O (oxygen) atoms
- FIG. 3B is a cross-sectional view of a plane containing atoms of B sites and O atoms.
- FIG. 4 is a diagram showing a surface structure of a SrTiO 3 (210) plane orientation substrate after annealing in the atmosphere at 1100 ° C. for 12 hours in an embodiment of the present invention.
- FIG. 4A is an AFM image of the surface of the annealed SrTiO 3 (210) plane orientation substrate
- FIG. 4B is a step portion extending in the in-plane [001] axial direction and a terrace portion of the (100) plane. It is a schematic sectional drawing of the surface structure which becomes.
- an atomic plane containing the rare earth element Ln, alkaline earth barium Ba, and oxygen O at the A site is laminated with LnO—MnO 2 —BaO—...
- 1 is a side view of a crystal lattice of an ordered LnBaMn 2 O 6 thin film.
- FIG. 5A is a side view as seen from the in-plane [001] axis
- FIG. 5B is a side view as seen from the in-plane [1-20] axis.
- Is a side view showing an enlarged part of SrTiO 3 (210) plane LnBaMn 2 O 6 film crystal lattice grown in the [100] axis direction in azimuth substrate in an embodiment of the present invention.
- the atomic planes of the rare earth element Ln and alkaline earth element Ba of the A site are laminated with LnO—MnO 2 —BaO... In the [210] axial direction, and the A site is ordered in the [100] axial direction.
- LnBaMn is a side view of the crystal lattice of the 2 O 6 film.
- FIG. 7A is a side view seen from the in-plane [001] axis
- FIG. 7B is a side view seen from the in-plane [1-20] axis. Is a side view showing an enlarged part of a comparative example SrTiO 3 (210) plane LnBaMn 2 O 6 film crystal lattice grown [210] axis direction in azimuth substrate.
- FIG. 1 shows a cross-sectional view of a thin film 3 formed on a substrate 2 which is a SrTiO 3 (210) plane orientation substrate.
- the thin film 3 is formed so as to cover at least a part of the surface of the substrate 2 in the (210) plane orientation.
- the resistance value in the film thickness direction is measured for the thin film 3.
- a 60 ⁇ m ⁇ Au—Pd electrode (not shown) is formed on the surface of the thin film 3 by sputtering.
- an Nb-doped SrTiO 3 (210) plane orientation substrate is adopted as the substrate 2, and an Al electrode (not shown) is vapor-deposited on the back surface of the substrate. These electrodes are used as measurement electrodes.
- the perovskite structure is expressed as ABO 3 , where A is the apex, B is the body center, and O (oxygen) is the face center.
- A is the apex
- B is the body center
- O oxygen
- the apex site is called the A site
- the atoms occupying the A site are called A atoms.
- the B-site atoms in the body center are also called B atoms. Note that the perovskite structure described in the present embodiment is described in cubic form only for the sake of simplicity.
- the perovskite structure included in the present embodiment in addition to cubic crystals, tetragonal (orthogonal), orthorhombic (orthorhombic), monoclinic (monoclinic), etc., the position of any crystal lattice with some deformation described above.
- A, B, and O atoms are arranged.
- a substance having a crystal structure in which a basic unit cell of a crystal lattice can be obtained only by connecting a plurality of the unit cells described above is also included in this embodiment.
- FIG. 2 is a side view showing a crystal lattice with a (210) plane orientation in a cubic perovskite structure common to the substrate 2 and the thin film 3.
- 2A is a side view as viewed from the in-plane [001] axis
- FIG. 2B is a side view as viewed from the in-plane [1-20] axis.
- the both side views of FIG. 2 are drawn with the substrate surface in the left-right direction of the paper surface and the direction perpendicular to the substrate surface ([210] axis; hereinafter referred to as “plane direction”) directed in the vertical direction of the paper surface. .
- plane direction the direction perpendicular to the substrate surface directed in the vertical direction of the paper surface.
- FIG. 3 is a sectional view showing the atomic arrangement in the (210) plane of each atomic layer, that is, in the substrate plane.
- the longitudinal direction of the paper is the in-plane [001] axis
- the horizontal direction is the in-plane [1-20] axis.
- the unit cell having a cubic perovskite structure with a (210) plane orientation employed in the present embodiment is formed to be inclined with respect to the substrate surface extending in the left-right direction in the figure.
- the (210) plane of the unit cell is parallel to the substrate surface, and the (100) plane forms about 26.6 degrees from the substrate surface ((210) plane) as shown in Equation 2.
- the arrangement of each atomic layer in the plane parallel to the substrate surface in the perovskite structure with the (210) plane orientation is as shown in FIG.
- the atomic planes of the AO atomic layer and the BO 2 atomic layer are alternately stacked in the direction perpendicular to the plane, such as AO—BO 2 —AO. .
- the interval in the perpendicular direction is 3d (210), that is, about 0.5238 nm.
- the length in the direction perpendicular to the plane in consideration of the in-plane atomic position periodicity is 5d (210), that is, about 0.873 nm.
- FIG. 3A shows an AO layer
- FIG. 3B shows a BO 2 layer
- SrTiO and substrate 2 is 3 (210) oriented substrate, the thin film 3 formed on the substrate 2 (210) plane, the same as that of the plane [001] lattice spacing in the axial direction (100) plane It is.
- the lattice spacing in the [1-20] axial direction in the plane is wider than that in the (100) plane.
- the central symmetry is essentially broken with respect to in-plane symmetry of the substrate surface (hereinafter referred to as “in-plane symmetry” only).
- SrTiO 3 (210) plane orientation substrate [1-2 Surface structure of SrTiO 3 (210) plane orientation substrate] Then, SrTiO 3 (210) oriented substrate plane in the surface of the substrate 2 is [001] of the first kind extending in the axial direction and a step portion caused by the surface orientation, a different orientation and its first type orientation
- the concavo-convex structure including the (100) plane terrace portion will be described.
- the surface of the SrTiO 3 (210) plane orientation substrate is not stepped at the purchase stage as in the case of the (100) plane orientation substrate of the same material. For this reason, the surface of the SrTiO 3 (210) plane orientation substrate at the purchase stage is flat on the nm scale, and no special regular structure is formed.
- a concavo-convex structure is formed on the surface of the substrate 2 obtained by annealing the SrTiO 3 (210) plane orientation substrate in this state in the atmosphere at a substrate arrival temperature of 1100 ° C. for 12 hours.
- This concavo-convex structure has a step portion extending in the in-plane [001] axial direction and a terrace portion having a (100) plane.
- FIG. 4 is a diagram showing the surface structure of the SrTiO 3 (210) plane orientation substrate after annealing in the atmosphere at 1100 ° C. for 12 hours.
- 4A is an AFM image of the surface of the substrate 2, which is an annealed SrTiO 3 (210) plane orientation substrate. Note that the AFM image is originally an image in which each pixel has a halftone, but on this paper surface, the halftone is expressed by the density of fine black and white pixels.
- FIG. 4B is a schematic cross-sectional view of the concavo-convex structure in the substrate 2 viewed from the in-plane [001] axis direction. As shown in FIG.
- a terrace portion 4 made of a (100) surface and a step portion 5 made of a (010) surface, that is, a first-type orientation surface are formed. Since such a concavo-convex structure was not observed in the SrTiO 3 (210) plane orientation substrate at the purchase stage, it can be said that this concavo-convex structure was formed by the above-described atmospheric annealing treatment.
- the thin film 3 that is the SmBaMn 2 O 6 thin film is formed using the terrace portion 4 formed of the (100) plane of the substrate 2 that is the SrTiO 3 (210) plane orientation substrate as a template.
- the thin film 3 it is possible to order SmO—MnO 2 —BaO—MnO 2 —SmO... And A site in the [100] axial direction.
- the thin film 3 is an SmBaMn 2 O 6 thin film formed on the surface of the concavo-convex structure of the substrate 2 which is a SrTiO 3 (210) plane orientation substrate by a laser ablation method.
- a laser ablation method first, as a target, for example, a SmBaMn 2 O 6 polycrystal produced by a solid-phase reaction method is formed into a cylindrical shape having a diameter of 20 mm and a length of 5 mm. Then, after attaching the substrate 2 after annealing in a vacuum chamber, evacuated to 3 ⁇ 10 -9 Torr (4 ⁇ 10 -7 Pa) or less.
- high-purity oxygen gas is introduced by 0.9 ⁇ 10 ⁇ 5 Torr (1.2 ⁇ 10 ⁇ 3 Pa), and Ar gas is added to bring the total pressure in the vacuum chamber to about 5 mTorr (0.67 Pa). adjust.
- the substrate 2 is heated to an ultimate temperature of 1040 ° C. in that atmosphere. Note that, as described above, the temperature reached by the substrate 2 during annealing (1100 ° C.) is higher than the temperature reached by the substrate 2 when the thin film 3 that is the SmBaMn 2 O 6 thin film is formed thereon.
- the concavo-convex structure on the surface of the substrate is not affected by substrate heating during film formation.
- the reason why the oxygen partial pressure and the total pressure are controlled independently is to apply the deposition conditions established so far when the SmBaMn 2 O 6 thin film in the present embodiment is produced.
- This point will be supplementarily described.
- the composition ratio of the formed thin film is required to be as constant as possible. This is because when a composition ratio shift occurs, excess elements are taken into the paired element, that is, the site of the counterpart, and the degree of order is inevitably lowered. An enormous amount of time is required to accurately determine the film forming conditions that can prevent the deterioration of the degree of order without any prior knowledge.
- a two-stage process is involved.
- first stage a pyramidal structure in which oxygen on the SmO plane is deficient is formed at a position where an oxygen octahedron is normally formed by using a huge ion radius of Ba ions.
- second stage is a stage in which oxygen deficient in the first stage is filled.
- the film formation conditions have been changed so as to simply lower the oxygen partial pressure.
- a change in conditions changes the plume shape in laser ablation.
- the plume is a balloon-like plasma generated in laser ablation, and in the plasma, an uneven composition cannot be avoided.
- the change in the plume shape caused by lowering the oxygen partial pressure changes the position where the plume collides with the substrate, causing a problem that the film forming conditions relating to the composition shift, that is, the composition shifts.
- the thin film 3 which is the SmBaMn 2 O 6 thin film of the present embodiment is controlled by controlling the oxygen partial pressure required thermodynamically and the total pressure maintaining the same plume shape peculiar to laser ablation independently of each other. Therefore, it is possible to apply the film formation conditions established so far in order to fabricate the film.
- the above-described two-stage film forming method in which the first step is performed while the oxygen partial pressure and the total pressure are controlled independently of each other is applied.
- the target is irradiated with a KrF excimer laser having a wavelength of 248 nm through the laser beam introduction port of the chamber to form an SmBaMn 2 O 6 thin film having a thickness of about 40 nm.
- RHEED reflection high-energy electron diffraction
- in-situ annealing is performed at 400 ° C. to fill the missing oxygen.
- the annealing atmosphere is performed by carefully adjusting the O 2 / Ar ratio so that the A-site order is not destroyed.
- the substrate 2 on which the thin film 3 has already been formed may be taken out of the vacuum chamber and then filled with oxygen by post-annealing. It has been confirmed that one of the suitable atmosphere gases in this case is N 2 O. This is because oxygen is filled without destroying the A-site ordering.
- Example samples were prepared according to the manufacturing method described above.
- the thin film 3 that is the SmBaMn 2 O 6 thin film is formed on the substrate 2 that is the SrTiO 3 (210) plane orientation substrate on which the above uneven structure is formed.
- the surface of the formed thin film 3 was observed by AFM in the example sample manufactured under the condition that the thin film 3 was thinner than the height difference of the uneven structure of the substrate 2. Then, similarly to the substrate 2, a concavo-convex structure having a step portion extending in the in-plane [001] axial direction and a terrace portion with a (100) plane was also confirmed on the surface of the thin film 3. Next, a reciprocal lattice space mapping measurement around (211) and (310) was performed by 4-axis X-ray diffraction. As a result, the thin film 3 was coherently grown on the substrate 2 even when grown in the [100] axis direction. It became clear that it became a crystal thin film. The ordering of the A sites was confirmed by the presence or absence of superlattice peaks by electron beam diffraction under a limited field of view using an electron microscope.
- FIG. 5 shows that the A site is ordered by taking a structure in which the atomic planes of the rare earth element Ln and the alkaline earth element Ba at the A site are laminated with LnO—MnO 2 —BaO—... In the [100] axis direction. It is the side view of the crystal lattice of converted LnBaMn 2 O 6 .
- FIG. 5A is an in-plane [001] axis
- FIG. 5B is a side view of the in-plane [1-20] axis. It is drawn by the same drawing method as a) and (b).
- the thin film 3 is different from the case of FIG. 2 in that it grows in the [100] axis direction and the A site is ordered.
- the charge trajectory alignment surface 1 in the thin film 3 on which such an A-site ordering pattern is formed has a direction inclined about 26.6 degrees which is parallel to the substrate as shown in FIG.
- FIG. 7 shows the structure of a thin film 13 which is a SmBaMn 2 O 6 thin film grown on a (210) plane-oriented substrate in the [210] axis direction and having an ordered A site.
- the illustration is based on LnBaMn 2 O 6 .
- [210] to grow toward the axial direction different from the case of the embodiment in which the pattern of A-site ordering in LnBaMn 2 O 6 film is shown in FIG.
- the charge trajectory alignment surface 11 of the thin film 13 is more inclined with respect to the substrate surface as shown in FIG.
- the charge trajectory alignment surface 11 is oriented at an angle of about 63.4 degrees with respect to the substrate surface.
- the SrTiO 3 (210) surface at the purchase stage which is flat on the nm scale is used.
- An orientation substrate is used.
- the step portion by the first type of orientation extending in the in-plane [001] axial direction and the first type of orientation are In contrast, by using a concavo-convex structure including a (100) plane terrace portion to grow a thin film on the (100) plane terrace, a thin film in which the charge orbit alignment surface 1 is arranged on the side parallel to the substrate surface can be obtained.
- the resistance was measured while increasing the temperature from room temperature (300K) to 400K, and it was confirmed that both samples obtained a clear resistance change that proved the primary transition due to charge orbit alignment near 390K.
- Nb-doped SrTiO 3 ( 210)
- the above two types of thin films produced in the same manner as in the above examples and comparative examples on a plane orientation substrate were used as measurement objects.
- measurement was performed without applying a magnetic field at room temperature (300 K), which is the charge orbit alignment phase, and the resistance value of the thin film with the example, that is, the charge orbit alignment surface parallel to the substrate surface, was the comparative example.
- a certain charge orbit alignment surface was about twice as large as that of the thin film whose side was perpendicular to the substrate surface.
- the electronic phase of SmBaMn 2 O 6 was transferred from the charge orbital alignment phase to the metal phase, and the resistance value was similarly measured.
- the resistance value at room temperature (300 K) when the external field is applied is smaller than the value before applying the magnetic field in both the example and the comparative example, and the thin film of the example is almost the same as the resistance value of the comparative example. Value. The inventor speculates that this is because the anisotropy due to the charge orbit alignment plane disappears in the metal phase induced by the application of the magnetic field.
- the properties of the thin film of the example and the comparative example as a resistance change amount between the resistance value in the charge orbit alignment phase, that is, the insulating phase in the absence of the magnetic field, and the resistance value when the metal phase is changed by the magnetic field. Contrasted.
- the resistance change amount varies depending on the arrangement orientation of the charge trajectory alignment surface with respect to the film thickness direction serving as a measurement current path, and the resistance change amount in the thin film of the example is larger than that in the comparative example. was confirmed.
- the atomic stacking plane is AO—BO 2. Since it becomes -AO, the A site can be ordered, and the in-plane symmetry is broken, so that the first order phase transition is possible.
- the charge orbit alignment surface is arranged on the side parallel to the base surface, so that the resistance value in the charge orbit alignment insulating phase is not reduced.
- the perovskite is used in the switching using the phase transition of the electronic phase such as generation and annihilation of the charge orbit alignment order at room temperature.
- the resistance change originally exhibited by the type manganese oxide can be used as much as possible even in the form of a thin film.
- the growth direction of the film is set to the [210] axis by utilizing the terrace portion of the concavo-convex structure formed by using the annealing treatment on the (210) oriented SrTiO 3 (210) plane orientation substrate. Controlled in direction.
- the same effect can be expected in the case of a (m10) -oriented (19 ⁇ m ⁇ 3) thin film. Therefore, the same effect as that of the present embodiment can be expected in all the substrates and thin films having the (m10) orientation (19 ⁇ m ⁇ 2).
- the materials, compositions, film thicknesses, formation methods, and the like of the thin film and the substrate exemplified in this embodiment are not limited to the above embodiments.
- the names of axes and planes for the perovskite crystal described for explanation can be expressed based on another equivalent expression as known to those skilled in the art. For example, even in the case where the crystal axis extending to the substrate surface is expressed as the [001] axis as in the above explanations, application of the crystal axis remains arbitrary and four equivalent arrangements can be considered. .
- a surface expressed as a (m10) plane by taking a certain axis with a right-handed system may be indexed with a (1m0) plane in a representation of another axis taking a right-handed system. . In this way, care must be taken that mutually equivalent planes become different expressions.
- the present invention can be used as a device using a perovskite-type manganese oxide thin film in which electrical, magnetic, and optical properties undergo a phase transition by temperature, electric field, magnetic field, or light irradiation to exhibit a switching phenomenon.
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Abstract
Description
θ1=arccos(1/(1+m2)1/2) 式1
にm=2を代入することにより求められ、そのθ1の値は約63.4度となる。その結果、絶縁体金属転移によって生じる電気的性質の変化を、膜厚方向の電気抵抗の変化として利用しようとする場合に、キャリアの流れる向きに近い向きに形成された電荷軌道整列面11が電流経路となってしまう。つまり、このような電荷軌道整列面の向きの場合には、絶縁体金属転移によりもたらされる抵抗変化が減少し、当該ペロフスカイト型マンガン酸化物薄膜をデバイスとして利用する場合に利用することができる抵抗変化が小さくなるという問題が懸念される。
θ=arctan(1/m) 式2
ここで、式1により算出される角度θ1と式2により算出される角度θとの間には、θ=(180-90-θ1)=(90-θ1)との関係が成り立つ。すなわち角度θ1と角度θは互いに余角(complementary angle)の関係にある。
本実施形態として例示のために説明するのは、(m10)面方位基板におけるm=2の場合に相当するSrTiO3による立方晶ペロフスカイト酸化物の基板(以下、「SrTiO3(210)面方位基板」という)である基板2の上に、基板2と格子ミスマッチの小さい立方晶ペロフスカイト型マンガン酸化物SmBaMn2O6(電荷軌道秩序温度約380K)を形成した薄膜3である。この具体例に基づいて、まず薄膜の構造について説明し、次いでその製造方法を説明し、その後に、実施例および比較例に基づき基板面に平行側に形成される電荷軌道整列面とその効果について説明する。
図1に、SrTiO3(210)面方位基板である基板2上に形成した薄膜3の断面図を示す。薄膜3は、基板2の(210)面方位の表面のうちの少なくとも一部を覆うように形成される。なお、後述するように薄膜3では、膜厚方向の抵抗値が測定される。このためには例えば、60μmφのAu-Pd電極(図示しない)をスパッタにより薄膜3の表面上に形成する。また、基板2としてNbドープSrTiO3(210)面方位基板を採用して、その基板の裏面にはAl電極(図示しない)を蒸着しておく。そして、これらの電極が測定用電極とされる。
次に、基板2および薄膜3に採用される立方晶ペロフスカイト構造における(210)面方位について説明する。ペロフスカイト構造はABO3と表記され、Aは頂点、Bは体心、O(酸素)は面心の各位置を占める。本実施形態の説明において、頂点のサイトをAサイトとよび、そこを占める原子をA原子と呼ぶ。体心のBサイトの原子も同様にB原子と呼ぶ。なお、本実施形態において説明するペロフスカイト構造を立方晶により説明しているのは単に説明の簡明さのためである。本実施形態に含まれるペロフスカイト構造には、立方晶以外にも、正方晶(tetragonal)、斜方晶(orthorhombic)、単斜晶(monoclinic)など、何らかの変形を伴う任意の結晶格子の位置に上述のA、B、O原子を配置しているものも含まれている。さらに、例えば、上述のユニットセルを複数つなげてはじめて結晶格子の基本単位格子が得られるような結晶構造の物質も、本実施形態に含まれている。
d(210)=a・sinθ 式3
から求められ、約0.1746nmとなる。なお、aはSrTiO3の格子定数(=0.3905nm)である。また、立方晶のユニットセルが(100)面方位から約26.6度傾いたという見方をすると、面直方向の間隔は3d(210)つまり約0.5238nmである。なお、面内原子位置周期性まで考慮した面直方向の長さは5d(210)つまり約0.873nmとなる。
次に、SrTiO3(210)面方位基板である基板2の表面における面内[001]軸方向に延びる第1種の向きの面によるステップ部と、その第1種の向きとは異なる向きの(100)面によるテラス部とを含む凹凸構造について説明する。SrTiO3(210)面方位基板の表面は、購入段階では同材料の(100)面方位基板の場合のようにはステップ出しがされていない。このため、購入段階のSrTiO3(210)面方位基板の表面は、nmスケールで平坦であり、特段の規則構造は形成されていない。ところが、その状態のSrTiO3(210)面方位基板を、大気中、基板到達温度1100℃、12時間の条件でアニール処理して得られた基板2の表面には凹凸構造が形成される。この凹凸構造は、面内[001]軸方向に延びるステップ部と(100)面のテラス部とを有している。
本実施形態においては、SrTiO3(210)面方位基板である基板2の(100)面からなるテラス部4をテンプレートとして、SmBaMn2O6薄膜である薄膜3を形成する。これにより、その薄膜3においては、[100]軸方向にSmO-MnO2-BaO-MnO2-SmO・・・とAサイトを秩序化させることが可能となる。
以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順、要素または部材の向きや具体的配置等は本発明の趣旨を逸脱しない限り適宜変更することかできる。したがって、本発明の範囲は以下の具体例に限定されるものではない。上述した製造方法に従って実施例サンプルを作製した。実施例サンプルは、上記凹凸構造を表面に形成したSrTiO3(210)面方位基板である基板2に、SmBaMn2O6薄膜である薄膜3を形成したものである。
次に、(100)面の作るテラス面上で[100]軸方向に成長したSmBaMn2O6薄膜である薄膜3のAサイト秩序と電荷軌道整列面1の配置について説明する。結晶格子の説明は、一般性を失わないためLnBaMn2O6に基づいて説明する。また、比較のため、成長方向が[210]軸である比較例についても説明する。
図5は、Aサイトの希土類元素Lnとアルカリ土類元素Baの原子面が[100]軸方向にLnO-MnO2-BaO-・・・と積層された構造を取ることによって、Aサイトが秩序化したLnBaMn2O6の結晶格子の側面図である。特に、図5(a)は面内[001]軸、図5(b)は、面内[1-20]軸からみた側面図であり、これらの図は、ペロフスカイト構造を説明した図2(a)および(b)と同様の作図法により描かれている。ただし、薄膜3では、[100]軸方向に成長しAサイトが秩序化している点は図2の場合と異なっている。このようなAサイト秩序化パターンが形成された薄膜3における電荷軌道整列面1は、図6に示すように基板に対して平行側となる約26.6度傾斜した向きとなる。
これに対し、同じ材質の薄膜であっても、成長方向が[210]軸である場合には電荷軌道整列面の向きは異なる。比較例として、(210)面方位基板上にて[210]軸方向に向かって成長し、Aサイトが秩序化したSmBaMn2O6薄膜である薄膜13の構造を図7に示す。ここでも、LnBaMn2O6に基づいて図示している。[210]軸方向に向かって成長すると、LnBaMn2O6薄膜におけるAサイト秩序化のパターンが図6に示した実施例の場合とは異なる。具体的には、薄膜13の電荷軌道整列面11は図8に示すように基板面に対してより大きく傾斜して、垂直側に配置される。この場合、電荷軌道整列面11が基板面に対して角度約63.4度に向くこととなる。なお、[210]軸方向に向かってSmBaMn2O6薄膜(LnBaMn2O6薄膜)を成長させるためには、ステップ出しがされていないもののnmスケールで平坦な購入段階のSrTiO3(210)面方位基板を用いる。
電荷軌道整列面の配置が異なる実施例サンプルと比較例サンプルの各薄膜がともに電荷軌道整列秩序の発生と消滅による一次転移を示すことを電気抵抗の温度依存性と磁場依存性とにより調べた。
11 電荷軌道整列面((210)面成長の場合)
2 基板
3 ペロフスカイト型マンガン酸化物薄膜
4 テラス:(100)面
5 ステップ:(010)面
13 ペロフスカイト型マンガン酸化物薄膜(比較例)
Claims (4)
- ペロフスカイト結晶格子のAサイトにバリウムBaと希土類元素Lnとを含んで構成されているペロフスカイト型マンガン(Mn)酸化物薄膜であって、
(m10)面方位(19≧m≧2)のペロフスカイト構造を有する基板の表面の少なくとも一部を覆って形成されており、
該基板の[100]軸方向に向かって、LnO-MnO2-BaO-MnO2-LnO・・・と積層された原子面を有している
ペロフスカイト型マンガン酸化物薄膜。 - 前記基板が(210)面方位の基板である
請求項1に記載のペロフスカイト型マンガン酸化物薄膜。 - 前記基板がSrTiO3(210)面方位基板であり、
該基板が、面内[001]軸方向に延びる第1種の向きの面によるステップ部と、前記第1種の向きとは異なる向きの(100)面によるテラス部とを含む凹凸構造を、前記ペロフスカイト型マンガン酸化物薄膜が形成される表面に有している
請求項2に記載のペロフスカイト型マンガン酸化物薄膜。 - 化学式SmBaMn2O6で表される
請求項1乃至請求項3のいずれか1項に記載のペロフスカイト型マンガン酸化物薄膜。
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