WO2012124506A1 - 酸化物基板およびその製造方法 - Google Patents
酸化物基板およびその製造方法 Download PDFInfo
- Publication number
- WO2012124506A1 WO2012124506A1 PCT/JP2012/055342 JP2012055342W WO2012124506A1 WO 2012124506 A1 WO2012124506 A1 WO 2012124506A1 JP 2012055342 W JP2012055342 W JP 2012055342W WO 2012124506 A1 WO2012124506 A1 WO 2012124506A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- lsat
- underlayer
- plane
- single crystal
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
- C30B23/025—Epitaxial-layer growth characterised by the substrate
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
- C30B1/023—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing from solids with amorphous structure
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/32—Titanates; Germanates; Molybdates; Tungstates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/68—Crystals with laminate structure, e.g. "superlattices"
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to an oxide substrate and a manufacturing method thereof. More particularly, the present invention relates to an oxide substrate having a planarized surface and a method for manufacturing the same.
- strongly correlated electron materials that cannot apply the band theory that supports the basics of semiconductor device design has also progressed. Among them, a substance showing a huge and high-speed property change due to a phase transition of an electronic system has been found.
- strongly correlated electron materials not only spin but also the degree of freedom of electron orbital is involved in the phase state of the electron system, and various electronic phases consisting of various orders formed by spin, charge, and orbital appear.
- a representative example of strongly correlated electron materials is perovskite-type manganese oxide, in which the charge-ordered phase in which 3d electrons of manganese (Mn) are aligned by the first-order phase transition, It is known that an orbital-ordered phase that aligns is expressed.
- 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. Further, the magnetic property of this electronic phase is an antiferromagnetic phase due to superexchange interaction and 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 metal phase there are various definitions of the metal phase, but here, “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 and orbital alignment phase: charge and orbital ordered phase)
- charge and orbital alignment phase charge and orbital ordered phase
- various switching phenomena are observed in a single crystal bulk material of the substance that can be taken (Patent Documents 1 to 3).
- 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.
- These switching phenomena are typically observed as huge changes in electrical resistance or transitions between the antiferromagnetic and ferromagnetic phases. For example, resistance changes of several orders of magnitude due to application of a magnetic field are well known as the giant magnetoresistance effect.
- the perovskite-type manganese oxide disclosed in each of the above-mentioned documents when the chemical composition is expressed as ABO 3 , the atomic lamination surface is a laminated layer in which AO layers, BO 2 layers, AO layers,. Become a body.
- the crystal structure of such a laminate is referred to as AO—BO 2 —AO.
- a trivalent rare earth cation hereinafter referred to as “Ln”
- a divalent alkaline earth (“Ae”) form the A site of the perovskite crystal structure. It is considered that the onset temperature of the switching phenomenon is lowered due to the randomness. If ions of A site, AeO-BO 2 -LnO-BO 2 -AeO-BO 2 -LnO-BO 2 - if it is possible to ... and ordered, up to about 500K and forth transition temperature to the charge ordering phase It is known that it can be raised.
- 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.
- JP-A-8-133894 Japanese Patent Laid-Open No. 10-255481 JP-A-10-261291 Japanese Patent Laid-Open No. 2005-213078
- the atomic stacking surface has a stacked structure of AO—BO 2 —AO.
- the (100) plane orientation substrate is a suitable substrate for ordering the A sites in the film thickness direction.
- Patent Document 4 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.
- the atomic lamination surface is a laminate of (Ln, Ba) BO—O 2 — (Ln, Ba) BO.
- This atomic layer stacking surface is formed as follows. First, an (Ln, Ba) BO layer, that is, a site (A site) expressed as (Ln, Ba) containing Ba atoms or rare earth elements Ln, an B layer, and O atoms is formed. Is done. Next, an atomic layer containing two O atoms is formed. Then, the (Ln, Ba) BO layer is formed again. In order to order the A site in this (Ln, Ba) BO—O 2 — (Ln, Ba) BO laminate, it is necessary to introduce regularity to the A site in the plane.
- the atomic lamination surface of the thin film formed on the surface of the (210) plane orientation substrate is a laminate of repeated atomic layers of AO—BO 2 —AO.
- the (210) plane orientation substrate is adopted, the A site can be ordered as in the case where the (100) plane orientation substrate is adopted.
- the symmetry in the plane of the substrate surface is broken, so that the first order transition phase transition is also possible. Therefore, the (210) plane orientation substrate is suitable for ordering the A site and achieving the possibility of the first-order transition phase transition.
- the lattice constant a 0.3905 nm is further considered in consideration of the lattice matching, that is, the small lattice mismatch.
- Strontium titanate (SrTiO 3 ) is selected.
- a single crystal substrate made of SrTiO 3 having a (210) plane-oriented surface is hereinafter referred to as “SrTiO 3 (210) plane single crystal substrate”.
- the present invention has been made in view of the above problems.
- the present invention contributes to the production of various devices using a perovskite-type manganese oxide thin film by providing an oxide substrate that maintains a flat surface at the atomic layer level even at a substrate temperature of around 1000 ° C. is there.
- the inventor of the present application others SrTiO 3 and the material (210) orientation single irregularities on the surface of the crystal substrate by focusing on the principle which is formed a result of examining the aforementioned problems, the SrTiO 3 (210) surface orientation surface It has been found that the formation of such irregularities can be suppressed by forming an underlayer of such a substance, particularly LSAT. That is, in an aspect of the present invention, a single crystal support substrate made of SrTiO 3 with a (210) plane orientation and (LaAlO 3 ) 0.3 formed on the surface of the (210) plane of the support substrate. There is provided an oxide substrate comprising-(SrAl 0.5 Ta 0.5 O 3 ) 0.7 or LSAT underlayer.
- the oxide substrate includes a substrate made of an oxide having a plurality of compositions in addition to an oxide substrate having a single composition.
- the oxide substrate when it is a single crystal substrate, it includes a substrate made of a plurality of materials that are single crystals in a region continuous over the plurality of materials.
- the support substrate crystal and the base layer crystal are crystals that are stacked on each other so as to be lattice-matched and continuous.
- a substrate composed of a substrate and a base layer is called a single crystal substrate.
- any of the aspects of the present invention even when a SrTiO 3 (210) -oriented single crystal substrate having a lattice constant suitable from the viewpoint of lattice matching is adopted as the support substrate, In addition, it becomes possible to keep the surface of the substrate flat in a temperature range for forming a thin film. This makes it possible to provide a suitable substrate for producing an A-site ordered perovskite-type manganese oxide thin film capable of primary phase transition.
- FIG. 3 is a schematic side view showing a state of inclination of a crystal lattice when a substrate or an underlayer has a (210) plane orientation in a single crystal substrate or an underlayer having a cubic perovskite structure in an embodiment of the present invention.
- FIG. 2A is a side view looking toward the in-plane [1-20] axis
- FIG. 2B is a side view looking toward the in-plane [001] axis.
- it is a flow chart showing a manufacturing method until a thin film is formed on a single crystal substrate, including a manufacturing method of a single crystal substrate.
- FIG. 4A is a RHEED pattern image photographed when the underlayer in an embodiment of the present invention is formed in a crystalline state
- FIG. 4A is a photographed RHEED pattern image
- FIG. 4B is easy to observe.
- it is the same RHEED pattern image that has undergone image processing that inverts only the contrast of the image.
- FIG. 1 is a schematic cross-sectional view of an oxide substrate having a support substrate and an underlayer in the first embodiment of the present invention.
- Oxide substrate of the present embodiment on the example (210) flush with the surface of the support substrate 1 of single crystal composed of a SrTiO 3 orientation, (LaAlO 3) 0.3 - ( SrAl 0.5 Ta 0. 5 O 3 ) 0.7, that is, a single crystal substrate 10 on which an LSAT single crystal underlayer 2 is formed.
- the foundation layer 2 formed as the present embodiment is the foundation layer 2 formed by crystallizing LSAT.
- This single crystal substrate 10 is used as an oxide substrate for forming another film in contact with the surface of the underlayer 2.
- an A-site ordered perovskite manganese oxide thin film 3 (hereinafter referred to as the thin film 3) is formed on the single crystal substrate 10.
- the underlayer in the present invention it is also possible to use the amorphous underlayer 2A of the LSAT component.
- the configuration will be described later as another embodiment (second embodiment).
- FIG. 2 is a schematic side view showing the inclination of the crystal lattice when the support substrate 1 or the underlayer 2 having the cubic perovskite structure is in the (210) plane orientation.
- SrTiO used for the support substrate 1 has a cubic perovskite structure.
- This cubic perovskite structure is a crystal structure that the support substrate 1, the underlayer 2, and the thin film 3 of this embodiment can take. For this reason, it demonstrates by the expression which does not lose generality.
- the perovskite structure is generally expressed as ABO 3, and in the unit cell, A occupies each position of the apex, B is the body center, and O (oxygen) is the face center.
- A occupies each position of the apex
- B is the body center
- O oxygen
- the apex site is referred to as an A site
- the atoms occupying the A site are referred to as 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 by cubic crystals in FIG. 2 merely 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.
- the crystal is drawn in such a direction that the support substrate surface and the underlayer surface extend in the left-right direction of the figure.
- the (210) plane of the crystal lattice that is, the plane including the [1-20] axis and the [001] axis direction is directed along the plane formed by the support substrate surface and the base layer surface.
- the [1-20] axis and the [001] axis are in-plane axes of the support substrate surface and the underlayer surface, an in-plane [1-20] axis and an in-plane [001] axis, respectively.
- the [210] axis is drawn in the vertical direction of the drawing toward the paper surface.
- the direction of the [210] axis is the normal direction since it is the normal direction of the surface of the support substrate and the surface of the underlayer.
- 2 (a) and 2 (b) are a side view of the crystal unit cell as viewed toward the in-plane [1-20] axis (FIG. 2 (a)) and the in-plane [001] axis. It is the side view (FIG.2 (b)) of the unit cell which tried.
- the angle formed by the substrate surface with respect to the (100) plane is about 26.56 degrees.
- atomic planes are alternately stacked with AO—BO 2 —AO.
- the value of d (210) is the surface spacing of SrO—TiO 2 —SrO in the SrTiO used for the support substrate 1, and is 0 when substituting about 3.905 nm for a and about 26.56 degrees for ⁇ . 1746 nm is obtained.
- FIG. 2A illustrates the spacing indicated by d (210) and 3 ⁇ d (210). Furthermore, the length in the direction perpendicular to the plane in consideration of the periodicity at the in-plane atom position is 0.873 nm which is 5 ⁇ d (210).
- interval shown by 3xd (210) shown to Fig.2 (a) is equivalent to the thickness from the AO atomic layer equivalent to a unit cell to the next AO atomic layer. Therefore, for the purpose of covering the surface of the support substrate 1 with the base layer 2, the base layer 2 is formed to have a thickness of 3 ⁇ d (210) or more. Thereby, it can prevent effectively that the surface of the support substrate 1 is exposed.
- FIG. 3 is a flowchart showing a manufacturing method until the thin film 3 is formed on the single crystal substrate 10 including the method for manufacturing the single crystal substrate 10.
- the support substrate 1 is prepared (S102). This is performed by holding the support substrate 1 cut in the (210) plane orientation of a single crystal made of SrTiO 3 in, for example, a vacuum chamber.
- the LSAT single crystal underlayer 2 is formed on the surface of the (210) plane of the support substrate 1 (S104).
- This formation is a process of depositing LSAT on the surface of the (210) plane of the support substrate 1 from the LSAT target facing the support substrate 1 by, for example, a laser ablation method.
- the support substrate 1 is appropriately heated so that the base layer 2 is formed as a single crystal coherently grown on the crystal of the support substrate 1.
- the single crystal substrate 10 is taken out from a vacuum chamber, for example, and stored as necessary.
- the thin film 3 is formed on the surface of the single crystal substrate 10 on which the LSAT base layer 2 is formed (S202).
- the underlayer 2 is a single crystal coherently grown on the crystal of the support substrate 1, the thin film 3 can be grown coherently on the single crystal substrate 10 as a whole.
- observation example 1 a change in the surface state of the substrate due to the temperature during film formation will be described as an observation example. Specifically, when a SrTiO 3 (210) -oriented single crystal substrate is adopted as the support substrate 1, the surface shape of the support substrate 1 was generated by annealing at several temperatures in the temperature range exceeding 1000 ° C. The change will be described as Observation Example 1. This annealing treatment is performed in order to reproduce the situation where the substrate is heated when the thin film 3 is formed coherently by laser ablation, for example.
- the SrTiO 3 (210) plane orientation single unit before the annealing process in a commercially available state is used.
- the surface state of the crystal substrate sample (referred to as “bare substrate sample”) was examined by AFM (atomic force microscope). When the surface of the bare substrate sample before the annealing treatment was observed by AFM, a hazy and unclear structure was observed, but the surface was flat on a sub-nm level scale.
- the bare substrate sample was annealed in the atmosphere at a substrate temperature of 1100 ° C. for 12 hours.
- the specular component of the RHEED pattern is not observed. Instead, it corresponds to the facet formation of the cubic crystal planes (100) and (010).
- An arrowhead diffraction pattern was observed at a position where a diffraction pattern consisting of streaks was observed (not shown).
- the surface of the bare substrate sample was observed by AFM, it was confirmed that an increased uneven structure having a height difference of about 3 nm was formed.
- the bare substrate sample was annealed at a temperature raised to 1180 ° C. Other time and atmosphere conditions remain unchanged. Then, the RHEED pattern did not change greatly, and it was confirmed that the height difference of the concavo-convex structure by AFM was further increased to about 6 nm.
- the difference in level of the concavo-convex structure developed by the annealing process at 1000 ° C. or 1100 ° C. on the surface of the support substrate 1 (bare substrate sample) with (210) orientation is expected in the normal step-and-terrace structure. This is much larger than the height difference.
- the height difference of about 3 nm or about 6 nm observed in the bare substrate sample can be said to be a large value that cannot be explained by the height difference caused by the step-and-terrace structure.
- the structure of the surface that is, the concavo-convex structure that causes the height difference that occurs when only the support substrate 1 is used, such as a bare substrate sample, is a structure that is clearly different from the conventional step / terrace structure.
- observation example 2 Next, in order to investigate the cause of the formation of the concavo-convex structure by the annealing treatment in the bare substrate sample, the influence of the similar annealing treatment was investigated as an observation example 2 using an oxide single crystal having a perovskite structure of another material.
- oxide single crystals it is known that a step-and-terrace structure with a miscut angle is formed on the surface by performing an annealing process under conditions of an atmospheric condition and around 1000 ° C. and a wet etching process using an acid. ing.
- the LSAT (210) substrate sample is observed by AFM prior to the annealing treatment, only a hazy and unclear structure is observed, and in particular, a step-and-terrace structure or an uneven structure with a larger elevation difference is not observed. It was. That is, the surface of the LSAT (210) substrate sample before annealing was similar to that of the support substrate 1 before annealing.
- the LSAT (210) substrate sample was annealed under the conditions of annealing in an air atmosphere at 1100 ° C. for 12 hours. A step terrace structure was formed on the surface of the LSAT (210) substrate sample as confirmed by AFM after the annealing treatment.
- the height difference due to the formed step-and-terrace structure was about 0.5 to 1 nm corresponding to an LSAT unit cell or twice that.
- the uneven structure such as the support substrate 1 before the annealing treatment causing the increased height difference is not observed in the LSAT (210) substrate sample.
- SrTiO 3 causes Sr deficiency at the internal A site, This is a state in which Sr (or SrO) is deposited on the surface, whereas LSAT is in a state in which such A site defects are not generated.
- the surface energy when the (100) plane is exposed is minimized when the size of the surface energy when each plane of the crystal structure of the perovskite structure is exposed to the surface is compared for each plane. For this reason, when Sr or SrO is deposited, the deposited Sr or SrO migrates on the surface by the thermal energy given by annealing, and either in the (100) plane or the equivalent (010) plane direction. Crystals grow while being deposited in the direction perpendicular to the surface. However, when the plane orientation is the (210) plane orientation, the crystal lattice of the internal atomic layer is asymmetric in the properties of the [1-20] axis direction and the [ ⁇ 120] axis direction.
- the growth rate differs between the (100) plane and the (010) plane, and as a result, an uneven structure with a height difference of several unit cells is generated.
- the concavo-convex structure is formed so as to extend in the [001] axial direction.
- the inventor of the present application applies an LSAT single crystal underlayer 2 to the support substrate 1 by laser ablation in advance on the support substrate 1 of the SrTiO 3 (210) substrate as shown in FIG. inspired to form as a cap layer.
- the process of forming the LSAT single crystal underlayer 2 at this time can be performed by a laser ablation method while sufficiently heating the support substrate 1 to a temperature such as an ultimate temperature of about 700 ° C., for example.
- the lattice constant of LSAT is 0.387 nm, and the lattice mismatch with the lattice constant a (0.3905 nm) of the SrTiO 3 (210) substrate is small.
- the LSAT single crystal can be coherently grown on the support substrate 1 which is a SrTiO 3 (210) substrate, and the in-plane lattice constant of the underlayer formed by the produced LSAT single crystal is also the same as the thickness of the LSAT single crystal.
- the single crystal substrate 10 composed of the support substrate 1 and the underlayer 2 must be suitable as a single crystal substrate for forming an A-site ordered perovskite-type manganese oxide thin film. Based on this idea, by actually forming the base layer 2 of the LSAT single crystal on the support substrate 1, two types of example samples of the single crystal substrate 10 were produced.
- the arrival of the support substrate 1 is a condition of the laser ablation method for depositing LSAT.
- a temperature of 700 ° C. and an oxygen partial pressure of 1 mTorr (0.133 Pa) were employed.
- the support substrate 1 is a SrTiO 3 (210) substrate.
- SrTiO 3 (210) it has been confirmed in advance that the surface flatness of the support substrate 1 by SrTiO 3 (210) is maintained at the same level as before heating at 700 ° C. substrate heating.
- the thickness of the base layer 2 of the LSAT single crystal formed on the support substrate 1 was determined by the following procedure. First, two thicknesses of 3 ⁇ d (210) corresponding to one unit cell and 15 ⁇ d (210) corresponding to five times the unit cell were adopted. Samples of the support substrate 1 of the SrTiO 3 (210) substrate on which the LSAT single crystal underlayer is formed with these thicknesses are used as the samples of the first and second examples, and these are the atmospheric air, the support substrate reached temperature of 1100 ° C., 12 Annealing was performed under the conditions of time. As a result, it was confirmed that in both of the samples of the first and second examples, an uneven structure having a height difference exceeding the height difference of the step / terrace structure was not generated at all.
- FIG. 4 is an RHEED pattern image taken when the underlayer 2 is formed in a crystalline state in the second embodiment sample.
- FIG. 4A is a photographed RHEED pattern image
- FIG. 4B is the same RHEED pattern image that has been subjected to image processing that reverses only the brightness of the image for easy observation. is there.
- On the paper surface each image expresses a halftone by the density of fine monochrome pixels.
- the RHEED pattern similar to that in FIG. 4 is also observed in the first example sample in which the base layer 2 is formed with a film thickness of 1 unit cell (3 ⁇ d (210)).
- FIG. 4 shows an RHEED pattern observed after forming the LSAT single crystal underlayer 2 at 700 ° C. and raising the temperature of the support substrate to 850 ° C.
- a diffraction pattern composed of Laue spots observed when the specular component or the surface is flat at the atomic level is clearly shown.
- the pattern shows that facets formed of the (100) plane and (010) plane corresponding to the arrowhead-shaped diffraction pattern and the resulting concavo-convex structure are not formed.
- the in-plane lattice of the LSAT underlayer 2 matches the lattice constant of the support substrate 1. It was also confirmed that Therefore, the underlayer 2 formed in a crystalline state has a flat surface without a step / terrace structure. This was also confirmed by separately observing with AFM (not shown). These points were the same in the sample of the first example.
- the LSAT layer functions as a cap layer serving as a SrO precipitation barrier that is Sr or its oxide, thereby suppressing the formation of a difference in level of the concavo-convex structure, and as a result, the flatness of the substrate surface was maintained even at high temperatures. Conceivable.
- a step / terrace structure may be formed in the underlayer 2 when the temperature is high (1100 ° C.).
- the resulting height difference is about 0.5 to 1 nm. Unlike the increased height difference of the bare substrate sample, it does not affect the subsequent formation of the thin film 3.
- the single crystal substrate 10 of this embodiment has an SrTiO having a suitable lattice constant from the viewpoint of small lattice mismatch when forming the thin film 3 which is a thin film of A-site ordered perovskite type manganese oxide.
- 3 (210) A substrate surface that maintains flatness even when heated to a temperature of 1000 ° C. or higher in the support substrate 1 that is a single crystal substrate.
- the single crystal substrate 10 employing the underlayer 2 is a single crystal that forms an A-site ordered perovskite-type manganese oxide thin film. Suitable as a crystal substrate.
- Employing the single crystal substrate 10 makes it possible to produce a good crystalline thin film of an A-site ordered perovskite-type manganese oxide thin film capable of primary phase transition.
- a substrate 10A that employs an amorphous base layer 2A in place of the base layer 2 in the first embodiment will be described.
- the material of the underlayer 2 ⁇ / b> A is LSAT similarly to the underlayer 2.
- the support substrate 1 is a single crystal support substrate having the same SrTiO 3 (210) plane orientation as that of the first embodiment.
- the substrate 10A has a layer configuration similar to that of the single crystal substrate 10, and as described above, only the state of the base layer 2A is made amorphous.
- FIG. 1 also shows the configuration of the substrate 10A.
- the method for manufacturing the substrate 10A of the present embodiment is also substantially the same as the method for manufacturing the single crystal substrate 10 described with reference to FIG.
- the temperature reached by the support substrate 1 in the process for forming the base layer 2A is, for example, from the manufacturing method of the substrate 10 of the first embodiment described above. Changed to 600 ° C. If the temperature at which the support substrate 1 is heated and reached during the formation process of the thin film 3 formed using the substrate 10A is sufficient to crystallize the base layer 2A, the base layer 2A In some cases, the thin film 3 is formed by crystallization by heating.
- FIG. 5 is an RHEED pattern image taken when the underlayer 2A is formed in an amorphous state in the third embodiment sample.
- FIG. 5A is a photographed RHEED pattern image
- FIG. 5B is the same RHEED pattern image that has been subjected to image processing that only reverses the brightness of the image for easy observation. It is.
- each image expresses a halftone by the density of fine monochrome pixels.
- the underlayer 2A was formed by laser ablation.
- the temperature reaches the support substrate 1 at which crystallization does not occur under the condition that the thickness corresponds to 5 times the unit cell.
- An amorphous LSAT underlayer 2A was formed at 600 ° C.
- the RHEED pattern shown in FIG. 5 clearly shows a halo pattern corresponding to the underlayer 2A formed on the support substrate 1 being in an amorphous state. Therefore, the underlayer 2A is in an amorphous state that does not contain any crystals.
- the sample of the third example was annealed in the atmosphere under the conditions of a support substrate reaching temperature of 850 ° C. and 12 hours.
- a diffraction pattern composed of specular components, Laue spots and streaks is observed in the RHEED pattern of the underlayer 2A once formed in an amorphous state. That is, in this annealing process at 850 ° C., the underlayer 2A started to crystallize.
- the lattice constant in the crystal of the underlying layer 2A formed in this manner matches that of the crystal lattice of the support substrate 1, and the distance between the Laue spot and the streak is the same as the surface of the support substrate 1 as described above. It was confirmed from the fact that it was the same as the interval in the diffraction pattern.
- Formation of thin film 3 when an amorphous underlayer is used The inventor uses, as a substrate on which the thin film 3 for achieving A-site ordering is formed, the crystallized underlayer 2 described in the first embodiment and the amorphous underlayer 2A described in the present embodiment. Both consider it available. That is, even when the substrate 10A of the amorphous base layer 2A is employed, the base layer 2A of the substrate 10A may be crystallized by subsequent heating based on the experimental results of the above-described third example sample. There is.
- the base layer 2A is formed by heat at the time of forming the thin film 3 on the surface. May crystallize. That is, with the configuration of the present embodiment, it is possible to proceed with crystallization of the underlayer 2A and formation of the thin film 3 simultaneously.
- the substrate 10A having the amorphous base layer 2A can be selected based on a certain guideline.
- the guideline is that the substrate 10A having the amorphous base layer 2A is used when the temperature reached by the support substrate 1 when forming the thin film 3 is higher than the temperature for crystallizing the amorphous base layer 2A. Is to do.
- the substrate 10A having the amorphous base layer 2A cannot be used because the temperature reached by the support substrate when forming the thin film 3 is higher than the temperature for crystallizing the amorphous base layer 2A. It can be said that it is low.
- the temperature at which the LSAT amorphous film starts to crystallize was about 800 ° C. or higher, for example, 850 ° C.
- the thin film 3 exceeds the temperature at which the crystallization starts, for example, when the thin film 3 is formed at a substrate temperature of around 1000 ° C., it is preferable to employ the amorphous underlayer 2A.
- the thin film 3 is formed by selecting the single crystal substrate 10 having the crystalline underlayer 2 described as the first embodiment, there is no suitable range for the temperature at the time of forming the thin film 3.
- the substrate 10A of this embodiment can also exhibit the same effects as the single crystal substrate 10 of the first embodiment. That is, when the thin film 3 which is a thin film of an A-site ordered perovskite type manganese oxide is formed, a substrate surface that maintains flatness even after being processed at a substrate temperature of about 1000 ° C. is provided. Further, since the LSAT underlayer 2A is also crystallized by heating, it is possible to form an LSAT single crystal underlayer whose in-plane lattice constant is exactly the same as that of SrTiO 3 .
- the present invention can be used as an oxide substrate for manufacturing a thin film device using a first-order phase transition due to charge orbital order at room temperature.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Thermal Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
[構造]
図1は、本発明の第1実施形態における支持基板と下地層とを有する酸化物基板の概略断面図である。本実施形態の酸化物基板は、例えば(210)面方位のSrTiO3からなる単結晶の支持基板1の一の表面の上に、(LaAlO3)0.3-(SrAl0.5Ta0.5O3)0.7すなわちLSATの単結晶の下地層2が形成されている単結晶基板10である。ここで、本実施形態として形成される下地層2は、LSATを結晶化して形成した下地層2である。この単結晶基板10は、下地層2の表面に接するようにして他の膜を形成するための酸化物基板として用いられる。例えば単結晶基板10には、Aサイト秩序化ペロフスカイト型マンガン酸化物の薄膜3(以下、薄膜3という)が形成される。なお、本発明における下地層としては、LSATの成分のアモルファス状態の下地層2Aを用いることも可能である。ただしその構成については別の実施形態(第2実施形態)として後述する。
d(210)=a・sinθ 式1
から求められる。このd(210)の値は、支持基板1に用いるSrTiOにおいてはSrO-TiO2-SrOという面の面間隔になり、aに約3.905nm、θに約26.56度を代入すると、0.1746nmが得られる。また、立方晶のユニットセルが(100)面方位から26.56度傾いたという見方をすると、面直方向の間隔は、3×d(210)である0.5238nmとなる。図2(a)には、d(210)および3×d(210)によって示されている間隔を例示している。さらに、面内原子位置における周期性まで考慮した面直方向の長さは5×d(210)である0.873nmとなる。
次に、上述した結晶構造の単結晶基板10の製造方法について説明する。図3は、単結晶基板10の製造方法を含み、単結晶基板10の上に薄膜3を形成するまでの製造方法を示すフローチャートである。単結晶基板10を製造するためには、まず支持基板1を準備する(S102)。これは、SrTiO3からなる単結晶の(210)面方位に切り出された支持基板1を、例えば真空槽内に保持することによって行なわれる。次に、LSATの単結晶の下地層2をその支持基板1の(210)面の表面の上に形成する(S104)。この形成は、例えばレーザーアブレーション法によって、支持基板1に対面させたLSATのターゲットから支持基板1の(210)面の表面にLSATを堆積させる処理である。この際、支持基板1の結晶にコヒーレントに成長した単結晶として下地層2が形成されるように、支持基板1は適宜加熱されている。これらの処理により単結晶基板10の製造が完了するため、必要に応じて単結晶基板10は例えば真空槽から取り出されて保管される。その後、必要に応じて単結晶基板10のLSATの下地層2が形成された面を対象に、薄膜3が形成される(S202)。下地層2が支持基板1の結晶にコヒーレントに成長した単結晶とされている場合には、薄膜3は、単結晶基板10全体を基板としてその上にコヒーレントに成長させることができる。
(観察例1)
次に、膜の形成時の温度による基板の表面状態の変化について、観察例として説明する。具体的には、支持基板1としてSrTiO3(210)面方位単結晶基板を採用した場合に、1000℃を超える温度域のいくつかの温度において、アニール処理によって支持基板1の表面形状に生じた変化について観察例1として説明する。このアニール処理は、例えばレーザーアブレーションによりコヒーレントに薄膜3を事後的に形成する際に、基板を加熱する状況を再現するために実施したものである。
次に、ベア基板サンプルにおいてアニール処理により上記凹凸構造が形成される原因を探るため、別の材質のペロフスカイト構造の酸化物単結晶により同様のアニール処理の影響を観察例2として調査した。一般に、酸化物の単結晶では、大気雰囲気、1000℃前後という条件のアニール工程と酸によるウエットエッチング工程とを施すことにより、表面にミスカット角によるステップ・テラス構造が形成されることが知られている。そこで、熱処理を行なうためのサンプルとして、(LaAlO3)0.3-(SrAl0.5Ta0.5O3)0.7すなわちLSATの市販されている基板を調査した。なお、LSAT基板の基板面方位は、上記の支持基板1と同じく(210)面方位である。この基板を以下LSAT(210)基板サンプルという。
以上の観察例1および2は、1000℃程度の温度下でのペロフスカイト酸化物の表面平坦性が物質に依存することを示している。そこで観察例1および2において、1000℃前後のアニールによりSrTiO3(210)基板サンプルにおいてのみ、数nmもの高低差の凹凸構造が形成される物理的機構を検討した。一般にSrTiO3(100)基板においては、大気中のアニールによりSrあるいはその酸化物であるSrOが表面に析出してくることが知られている。一方、LSAT(100)基板ではそのような析出現象は報告されていない。これらからいえることは、大気中での酸素分圧とアニール温度によって定まる熱平衡条件下において熱力学的に安定となるのが、SrTiO3では内部のAサイトにSrの欠損を生じさせ、その分のSr(またはSrO)を表面に析出させる状態であるのに対し、LSATではそのようなAサイトの欠損を生成しない状態である、ということである。
これに対して、LSAT(210)面方位基板で単結晶基板の表面が平坦に維持される理由は次の通りである。LSAT(210)面方位基板では、上記SrあるいはSrOのような初期のきっかけとなる析出層が生じない。このため、異方的に(100)面あるいは(010)面が成長することはない。そうすると、たとえ高温下であったとしても、ユニットセルのステップを超える凹凸が生成されることはない。
本願の発明者は、上述した考察に基づいて、図1に示すようにSrTiO3(210)基板の支持基板1上に、あらかじめレーザーアブレーション法によりLSAT単結晶の下地層2を、支持基板1に対するキャップ層として形成することを着想した。この際のLSAT単結晶の下地層2を形成する処理は、支持基板1を、例えば700℃程度の到達温度といった温度に十分に加熱しながらのレーザーアブレーション法によって実施することができる。ここで、LSATの格子定数は0.387nmであり、SrTiO3(210)基板の格子定数a(0.3905nm)との間の格子ミスマッチが小さい。このため、LSAT単結晶はSrTiO3(210)基板である支持基板1にコヒーレントに成長させることが可能であり、作製したLSAT単結晶による下地層の面内格子定数も、LSAT単結晶の厚みが薄い場合にはSrTiO3と全く同一にすることが可能となる。すなわち、支持基板1と下地層2からなる単結晶基板10は、Aサイト秩序ペロフスカイト型マンガン酸化物薄膜を形成する単結晶基板として好適となるに違いない。このような考えに基づいて、実際にLSAT単結晶の下地層2を支持基板1に形成することにより、単結晶基板10の実施例サンプルを2種作製した。
第1および第2実施例サンプルにおいては、LSAT単結晶の下地層2を支持基板1の一方の面に接して形成するために、LSATを堆積させるレーザーアブレーション法の条件として、支持基板1の到達温度700℃、酸素分圧1mTorr(0.133Pa)を採用した。支持基板1はSrTiO3(210)基板である。なお、700℃の基板加熱では、SrTiO3(210)による支持基板1の表面平坦性が加熱される前と同程度に保たれていることをあらかじめ確認している。
[構造]
次に、本発明の第2実施形態として、第1実施形態における下地層2に代えて、アモルファス状態の下地層2Aを採用する基板10Aについて説明する。下地層2Aの材質は、下地層2と同様にLSATである。また、支持基板1は、第1実施形態と同様のSrTiO3(210)面方位の単結晶支持基板である。
基板10Aの構成を有する実施例サンプル(第3実施例サンプル)を作製した。図5は、第3実施例サンプルにおいて下地層2Aをアモルファス状態で形成する際に撮影したRHEEDパターン像である。このうち、図5(a)は撮影されたRHEEDパターン像であり、図5(b)は観察を容易にするために、像の明暗を反転させるのみの画像処理を行なった同一のRHEEDパターン像である。また、図4と同様に、紙面においては、各像とも、微細な白黒画素の密度により中間調を表現している。第3実施例サンプルにおいても、レーザーアブレーションにより下地層2Aの形成処理を行なった。具体的には、仮に結晶化してLSATの下地層を形成するとした場合には5倍のユニットセルに相当する厚みとなるような条件によって、結晶化が起らない支持基板1の到達温度である600℃にてアモルファスのLSATの下地層2Aを形成した。
発明者は、Aサイト秩序化を達成する薄膜3を形成する基板として、第1実施形態にて上述した結晶化された下地層2と本実施形態にて説明したアモルファス状態の下地層2Aとの双方が利用可能であると考えている。つまり、アモルファス状態の下地層2Aの基板10Aを採用した場合であっても、上述した第3実施例サンプルの実験結果から、基板10Aの下地層2Aは事後的な加熱によって結晶化される可能性がある。このため、薄膜3を形成する際の温度によっては、基板10Aの下地層としてたとえアモルファス状態の下地層2Aを採用しても、その面の上に薄膜3を形成する際の熱によって下地層2Aが結晶化する可能性がある。すなわち、本実施形態の構成により下地層2Aの結晶化と薄膜3の形成を同時に進行させることが可能となる。
アモルファス状態の下地層2Aを有する基板10Aは、ある指針に基づいて選択することができる。その指針とは、薄膜3を形成する際の支持基板1の到達温度がアモルファス状態の下地層2Aを結晶化するための温度よりも高い場合に、アモルファス状態の下地層2Aを有する基板10Aを採用する、というものである。言い換えるなら、アモルファス状態の下地層2Aを有する基板10Aを採用することできないのは、薄膜3を形成する際の支持基板の到達温度が、アモルファス状態の下地層2Aを結晶化するための温度よりも低い場合、ともいえる。なお、発明者が別途検討した結果からは、LSATのアモルファスの膜が結晶化を開始する温度は、800℃程度かそれより高温、例えば850℃であった。このため、薄膜3が、その結晶化を開始する温度を超える場合、例えば1000℃前後の基板温度において形成される場合には、アモルファス状態の下地層2Aを採用することが好適である。ちなみに、第1実施形態として説明した結晶性の下地層2を有する単結晶基板10を選択して薄膜3を形成する場合には、薄膜3の形成時の温度に好適な範囲はない。
10A 基板
1 SrTiO3(210)面方位単結晶支持基板
2 下地層(LSAT単結晶)
2A 下地層(アモルファス状態のLSAT)
3 薄膜
Claims (8)
- (210)面方位のSrTiO3からなる単結晶の支持基板と、
該支持基板の(210)面の表面の上に形成された(LaAlO3)0.3-(SrAl0.5Ta0.5O3)0.7すなわちLSATの下地層と
を備える
酸化物基板。 - 前記LSATの下地層の厚みが、LSATの(210)面の面間隔をd(210)として、3×d(210)以上である
請求項1に記載の酸化物基板。 - 前記LSATの下地層が結晶状態に形成されている
請求項1に記載の酸化物基板。 - 前記LSATの下地層がアモルファス状態に形成されている
請求項1に記載の酸化物基板。 - (210)面方位のSrTiO3からなる単結晶の支持基板を準備するステップと、
(LaAlO3)0.3-(SrAl0.5Ta0.5O3)0.7すなわちLSATの下地層を、該支持基板の(210)面の表面の上に形成するステップと
を含む
酸化物基板の製造方法。 - 前記LSATの下地層の厚みが、LSATの(210)面の原子層の間隔をd(210)として、3×d(210)以上である
請求項5に記載の酸化物基板の製造方法。 - 前記LSATの下地層を形成するステップが、LSATの下地層が結晶状態に形成される支持基板温度にて実施される
請求項5に記載の酸化物基板の製造方法。 - 前記LSATの下地層を形成するステップが、LSATの下地層がアモルファス状態に形成される支持基板温度にて実施される
請求項5に記載の酸化物基板の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137003649A KR20130139856A (ko) | 2011-03-14 | 2012-03-02 | 산화물 기판 및 그 제조 방법 |
CN201280002392.4A CN103069056B (zh) | 2011-03-14 | 2012-03-02 | 氧化物基材及其制备方法 |
DE112012001262.3T DE112012001262T5 (de) | 2011-03-14 | 2012-03-02 | Oxidsubstrat und Verfahren zu dessen Herstellung |
JP2013504649A JP5590218B2 (ja) | 2011-03-14 | 2012-03-02 | 酸化物基板およびその製造方法 |
US13/765,156 US8524382B2 (en) | 2011-03-14 | 2013-02-12 | Oxide substrate and manufacturing method therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-055006 | 2011-03-14 | ||
JP2011055006 | 2011-03-14 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/765,156 Continuation US8524382B2 (en) | 2011-03-14 | 2013-02-12 | Oxide substrate and manufacturing method therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012124506A1 true WO2012124506A1 (ja) | 2012-09-20 |
Family
ID=46830581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/055342 WO2012124506A1 (ja) | 2011-03-14 | 2012-03-02 | 酸化物基板およびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8524382B2 (ja) |
JP (1) | JP5590218B2 (ja) |
KR (1) | KR20130139856A (ja) |
CN (1) | CN103069056B (ja) |
DE (1) | DE112012001262T5 (ja) |
WO (1) | WO2012124506A1 (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2650407B1 (en) * | 2010-12-09 | 2015-07-29 | Fuji Electric Co., Ltd. | Perovskite manganese oxide thin film |
EP2698455A4 (en) * | 2011-04-14 | 2014-12-03 | Fuji Electric Co Ltd | PEROVSKITMANGANOXID-THIN FILM |
US9070816B2 (en) * | 2011-05-19 | 2015-06-30 | Fuji Electric Co., Ltd. | Thermoelectric conversion structure and method of manufacturing same |
KR20140082653A (ko) * | 2011-10-19 | 2014-07-02 | 후지 덴키 가부시키가이샤 | 강상관 비휘발 메모리 소자 |
US20140272684A1 (en) | 2013-03-12 | 2014-09-18 | Applied Materials, Inc. | Extreme ultraviolet lithography mask blank manufacturing system and method of operation therefor |
US9354508B2 (en) | 2013-03-12 | 2016-05-31 | Applied Materials, Inc. | Planarized extreme ultraviolet lithography blank, and manufacturing and lithography systems therefor |
US9632411B2 (en) | 2013-03-14 | 2017-04-25 | Applied Materials, Inc. | Vapor deposition deposited photoresist, and manufacturing and lithography systems therefor |
US9612521B2 (en) | 2013-03-12 | 2017-04-04 | Applied Materials, Inc. | Amorphous layer extreme ultraviolet lithography blank, and manufacturing and lithography systems therefor |
US9417515B2 (en) | 2013-03-14 | 2016-08-16 | Applied Materials, Inc. | Ultra-smooth layer ultraviolet lithography mirrors and blanks, and manufacturing and lithography systems therefor |
CN114774844A (zh) * | 2022-03-31 | 2022-07-22 | 清华大学 | 在原子级别调控薄膜平整表面成分的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001278700A (ja) * | 2000-03-29 | 2001-10-10 | Canon Inc | ナノ構造体、その製造方法および磁気デバイス |
JP2005213078A (ja) * | 2004-01-28 | 2005-08-11 | Sharp Corp | ペロブスカイトマンガン酸化物薄膜及び該薄膜を備えてなるスイッチング素子、並びに該薄膜の製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5691279A (en) * | 1993-06-22 | 1997-11-25 | The United States Of America As Represented By The Secretary Of The Army | C-axis oriented high temperature superconductors deposited onto new compositions of garnet |
JP2685721B2 (ja) | 1994-11-04 | 1997-12-03 | 工業技術院長 | 無粒界型マンガン酸化物系結晶体及びスイッチング型磁気抵抗素子 |
JP3030333B2 (ja) | 1997-03-14 | 2000-04-10 | 工業技術院長 | 電流及び電場誘起相転移を用いたスイッチング素子及びメモリー素子 |
JP3012902B2 (ja) | 1997-03-18 | 2000-02-28 | 工業技術院長 | 光誘起相転移を用いたスイッチング素子及びメモリー素子 |
US20040069991A1 (en) * | 2002-10-10 | 2004-04-15 | Motorola, Inc. | Perovskite cuprate electronic device structure and process |
US8032196B2 (en) * | 2006-08-23 | 2011-10-04 | Chugoku Electric Power Co., Inc. | Josephson device, method of forming Josephson device and superconductor circuit |
-
2012
- 2012-03-02 WO PCT/JP2012/055342 patent/WO2012124506A1/ja active Application Filing
- 2012-03-02 JP JP2013504649A patent/JP5590218B2/ja not_active Expired - Fee Related
- 2012-03-02 DE DE112012001262.3T patent/DE112012001262T5/de not_active Withdrawn
- 2012-03-02 KR KR1020137003649A patent/KR20130139856A/ko not_active Application Discontinuation
- 2012-03-02 CN CN201280002392.4A patent/CN103069056B/zh not_active Expired - Fee Related
-
2013
- 2013-02-12 US US13/765,156 patent/US8524382B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001278700A (ja) * | 2000-03-29 | 2001-10-10 | Canon Inc | ナノ構造体、その製造方法および磁気デバイス |
JP2005213078A (ja) * | 2004-01-28 | 2005-08-11 | Sharp Corp | ペロブスカイトマンガン酸化物薄膜及び該薄膜を備えてなるスイッチング素子、並びに該薄膜の製造方法 |
Non-Patent Citations (1)
Title |
---|
LI,Y. ET AL.: "Dependence of crystallinity on oxygen pressure and growth mode of La0,3Sr1.7A1TaO6 thin films on different substrates.", JOURNAL OF APPLIED PHYSICS, vol. 87, 2000, pages 3707 - 3710 * |
Also Published As
Publication number | Publication date |
---|---|
DE112012001262T5 (de) | 2014-01-02 |
JP5590218B2 (ja) | 2014-09-17 |
KR20130139856A (ko) | 2013-12-23 |
CN103069056B (zh) | 2015-11-25 |
CN103069056A (zh) | 2013-04-24 |
US20130149528A1 (en) | 2013-06-13 |
JPWO2012124506A1 (ja) | 2014-07-17 |
US8524382B2 (en) | 2013-09-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5590218B2 (ja) | 酸化物基板およびその製造方法 | |
Hao et al. | A comprehensive review on the progress of lead zirconate-based antiferroelectric materials | |
JP6053879B2 (ja) | 強誘電体薄膜 | |
US10243134B2 (en) | Piezoelectric film and piezoelectric ceramics | |
JP2007099618A (ja) | 強誘電体薄膜 | |
JP2000208828A (ja) | 圧電体薄膜素子およびその製造方法 | |
WO2022168800A1 (ja) | 積層構造体及びその製造方法 | |
JP5720698B2 (ja) | ペロフスカイト型マンガン酸化物薄膜 | |
JP5692365B2 (ja) | ペロフスカイト型マンガン酸化物薄膜 | |
JP5725036B2 (ja) | ペロフスカイト型マンガン酸化物薄膜およびその製造方法 | |
JP2001172100A (ja) | エピタキシャル複合構造体およびこのものを利用した素子 | |
JP4142128B2 (ja) | 積層薄膜およびその製造方法 | |
Bae et al. | Novel sol-gel processing for polycrystalline and epitaxial thin films of La 0.67 Ca 0.33 MnO 3 with colossal magnetoresistance | |
JP4230368B2 (ja) | ペロブスカイトマンガン酸化物膜及びその製造方法 | |
JP2004006960A (ja) | 誘電体膜の形成方法 | |
Nakamura et al. | BiFeO3 Thin Films Prepared by Chemical Solution Deposition with Approaches for Improvement of Ferroelectricity | |
KR100717960B1 (ko) | 초전도 전극을 이용한 나노스토리지 강유전체 매체구조 및그 제조방법 | |
Yoshida et al. | Fabrication and Characterization of BaTiO3/Pt/C/Pt/Ti/SiO2 structures |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201280002392.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12758386 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013504649 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20137003649 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 112012001262 Country of ref document: DE Ref document number: 1120120012623 Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12758386 Country of ref document: EP Kind code of ref document: A1 |