WO2014091968A1 - Procédé de production de monocristal, et monocristal produit à l'aide dudit procédé - Google Patents

Procédé de production de monocristal, et monocristal produit à l'aide dudit procédé Download PDF

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WO2014091968A1
WO2014091968A1 PCT/JP2013/082493 JP2013082493W WO2014091968A1 WO 2014091968 A1 WO2014091968 A1 WO 2014091968A1 JP 2013082493 W JP2013082493 W JP 2013082493W WO 2014091968 A1 WO2014091968 A1 WO 2014091968A1
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single crystal
film
producing
seed substrate
zno
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PCT/JP2013/082493
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English (en)
Japanese (ja)
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守道 渡邊
克宏 今井
吉川　潤
潔 松島
聡太 大河内
七瀧　努
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日本碍子株式会社
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Priority to JP2014551993A priority Critical patent/JPWO2014091968A1/ja
Publication of WO2014091968A1 publication Critical patent/WO2014091968A1/fr

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    • 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
    • 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
    • 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
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing

Definitions

  • the present invention relates to a method for producing a single crystal. More specifically, the present invention relates to a method for producing a single crystal that can produce a homogeneous single crystal with few pores with high productivity. Furthermore, the present invention also relates to a single crystal produced by the method.
  • piezoelectric materials used for piezoelectric actuators used in various applications such as piezoelectric pumps and ink-jet printer ink heads, and various semiconductor elements such as light-emitting diodes (LEDs) and laser diodes (LDs).
  • LEDs light-emitting diodes
  • LDs laser diodes
  • various inorganic materials such as ceramics are used. In order to improve the performance of such inorganic materials, it is known that it is important to increase the degree of crystal orientation in these inorganic materials.
  • polarization process a process for aligning the direction of electric dipoles in the crystal by applying an electric field to the piezoelectric ceramics (polarization process) is performed.
  • a method for forming a single crystal film or an alignment film including a polycrystalline film in which crystals are oriented to some extent (hereinafter, sometimes referred to as “orientation polycrystalline film”)
  • a raw material melt for an oriented polycrystalline film is prepared and crystallized on a seed single crystal.
  • raw materials such as oxides (such as zinc oxide (ZnO)), nitrides (such as gallium nitride (GaN)), and carbides (such as silicon carbide (SiC) used in such a method are extremely May have a high melting point or may be easily decomposed.
  • a Na flux method has been proposed in which a raw material is dissolved using sodium (Na) as a flux and precipitated into seeds to obtain a single crystal (for example, Patent Documents). 1).
  • a GaN layer is formed on a heterogeneous substrate such as sapphire using a hydride vapor phase epitaxy, and the heterogeneous substrate is removed after the growth of the GaN layer, whereby a self-standing GaN single crystal substrate is formed.
  • a method of obtaining is proposed (see, for example, Patent Document 2).
  • these prior art methods have the problem that the crystal growth rate is slow.
  • Patent Documents 3 and 4 as one method for producing a crystal, the contact portion is heated while the sintered body and the single crystal (seed substrate) are in contact with each other, and the other ends are also produced. It is disclosed that a predetermined temperature gradient is generated by performing temperature control for cooling a portion, and a polycrystalline sintered body is single-crystallized or oriented starting from a seed substrate (for example, Patent Document 3). 4 and FIG. 4 of Patent Document 4).
  • the seed is grown.
  • the substrate surface is mirror-polished, the sintered body and the seed substrate are pressed into contact with each other, or a liquid phase material is filled in the interface so that there is no void at the interface between the two, and the two are brought into close contact with each other.
  • This is very important. This complicates the manufacturing process and the manufacturing apparatus. In particular, it is extremely difficult to make a large-area sintered body and the seed substrate adhere to each other uniformly.
  • a predetermined temperature gradient is generated by heating the contact portion between the polycrystalline sintered body and the seed substrate and cooling the other end region of the sintered body.
  • the temperature gradient is small, solid phase growth occurs at the interface between the sintered body and the seed substrate, but grain growth proceeds separately in each particle within the sintered body that is distant from the interface.
  • the particles taken into the seed crystal become coarse, and finally the solid phase growth stops.
  • coarse particles are separately taken into the seed crystal, pores are likely to remain in the film.
  • the temperature gradient is excessive to prevent such a problem, the workpiece itself may be damaged.
  • the particle size of the raw material powder is increased by the aerosol deposition method (hereinafter sometimes referred to as “AD method”) so that the particle size gradually increases with distance from the seed substrate.
  • AD method aerosol deposition method
  • the manufacturing method of the single crystal film and the oriented polycrystalline film according to the above prior art is very complicated as described above and takes time.
  • it is added to the film of raw material powder to shift the solid solution impurities mixed in the raw material powder and the orientation temperature to the lower temperature side in order to control the direction of solid phase growth and control the orientation of crystal grains.
  • It is extremely difficult to accurately control the concentration distribution of the sintering aid in the film as intended, and it is difficult to obtain homogeneous crystals.
  • the particles existing in the region away from the interface between the film and the seed substrate grow into coarse particles by heat treatment. A great deal of energy is required and eventually solid phase growth stops.
  • coarse particles are taken in separately, pores tend to remain in the film.
  • the present invention has been made to meet such a demand. That is, the present invention is excellent in productivity capable of producing a high-quality single crystal with few pores not only in a material system that is easy to obtain a raw material melt but also in a material system that is difficult to obtain a raw material melt. Another object is to provide a single crystal manufacturing method.
  • One object of the present invention is to A film forming step for forming a film on the surface of the seed substrate; and a heating step for obtaining a single crystal by heating the film formed on the surface of the seed substrate;
  • a method for producing a single crystal comprising: A film thickness that is a thickness in a direction perpendicular to the surface of the seed substrate of the film formed in the film forming step is 100 ⁇ m or less; The film is heated from the side of the seed substrate in the heating step, and the heating rate of the film in the heating step is 30 ° C./min or more, It is achieved by a single crystal manufacturing method characterized by the following.
  • the method for producing a single crystal according to the present invention not only a material system that is easy to obtain a raw material melt, but also a high quality single crystal that has few pores in a material system that is difficult to obtain a raw material melt. It can be produced with high productivity.
  • the present invention has been made to meet such a demand. That is, the present invention is excellent in productivity capable of producing a high-quality single crystal with few pores not only in a material system that is easy to obtain a raw material melt but also in a material system that is difficult to obtain a raw material melt. Another object is to provide a single crystal manufacturing method.
  • the present inventor first formed a film having a thickness of a predetermined value or less on a seed substrate, and the film thus obtained is not less than a predetermined value from the seed substrate side.
  • High-quality single crystals with few pores are high not only in material systems where it is easy to obtain a raw material melt but also in material systems where it is difficult to obtain a raw material melt.
  • the inventors have found that it can be produced with productivity, and have come up with the present invention.
  • the first embodiment of the present invention is: A film forming step for forming a film on the surface of the seed substrate; and a heating step for obtaining a single crystal by heating the film formed on the surface of the seed substrate;
  • a method for producing a single crystal comprising: A film thickness that is a thickness in a direction perpendicular to the surface of the seed substrate of the film formed in the film forming step is 100 ⁇ m or less; The film is heated from the side of the seed substrate in the heating step, and the heating rate of the film in the heating step is 30 ° C./min or more, Is a method for producing a single crystal.
  • the method for manufacturing a single crystal according to the present embodiment includes a film forming step for forming a film on the surface of the seed substrate, and a single crystal by heating the film formed on the surface of the seed substrate.
  • a heating method for obtaining a single crystal is also in this technical field, as described above, for example, the raw material powder is sprayed and deposited on the seed substrate by the AD method (corresponding to the film forming step in the single crystal manufacturing method according to this embodiment).
  • the AD method corresponding to the film forming step in the single crystal manufacturing method according to this embodiment.
  • It has already been proposed to produce a single crystal film by heat-treating the film containing the raw material formed in this way (corresponding to the heating step in the single crystal production method according to this embodiment) (for example, see Patent Document 5). reference).
  • the conventional single crystal manufacturing methods including the above are complicated in process, difficult to obtain homogeneous crystals, and difficult to suppress the generation of pores. In reality, it is difficult to produce high-quality single crystals with few pores with high productivity.
  • a film having a thickness of a predetermined value or less is formed on the seed substrate, and the film thus obtained is increased from the seed substrate side by a predetermined value or more.
  • Heat at temperature rate Specifically, in the single crystal manufacturing method according to the present embodiment, as described above, first, in the film forming step, a film having a thickness of 100 ⁇ m or less in the direction perpendicular to the surface of the seed substrate is seeded. Next, in the heating step, the film formed on the surface of the substrate is heated from the seed substrate side, and the film is heated at a temperature increase rate of 30 ° C./min or more. .
  • the single crystal manufacturing method according to this embodiment not only a material system that is easy to obtain a raw material melt, but also a material system that is difficult to obtain a raw material melt has a high quality with few pores.
  • a single crystal can be produced with high productivity.
  • the main component of the substance for obtaining a single crystal by the single crystal manufacturing method according to the present embodiment is not particularly limited, and examples thereof include various ceramics, oxides such as zinc oxide (ZnO) and titanium oxide (TiO 2 ), And nitrides such as gallium nitride (GaN) (details will be described later).
  • the film thickness (which is the thickness in a direction perpendicular to the surface of the seed substrate) formed on the surface of the seed substrate in the film forming step included in the method for manufacturing a single crystal according to this embodiment is 100 ⁇ m or less. It is desirable that the thickness is 30 ⁇ m or less.
  • the temperature rising rate of the film in the heating step included in the method for producing a single crystal according to this embodiment is desirably 30 ° C./min or more, and more desirably 300 ° C./min or more.
  • the second embodiment of the present invention provides: A method for producing a single crystal according to the first embodiment of the present invention, comprising: The film formed in the film forming step has a thickness of 30 ⁇ m or less; Is a method for producing a single crystal.
  • the third embodiment of the present invention A method for producing a single crystal according to any one of the first and second embodiments of the present invention,
  • the heating rate of the film in the heating step is 300 ° C./min or more, Is a method for producing a single crystal.
  • the method of forming a film on the surface of the seed substrate in the film forming step included in the method for producing a single crystal according to the present invention has good adhesion to the seed substrate and is in the film (micron order (ie, There is no particular limitation as long as it is possible to form a dense film (with a size of 1 ⁇ m or more) that does not generate pores on the seed substrate.
  • the powder is sprayed toward a target substrate or the like to solidify the powder on the substrate.
  • Powder method for forming a film solution method for forming a film by depositing or coating the main component and / or precursor on the surface of a substrate using a solution containing the main component and / or precursor of the film, physical vapor deposition
  • the film may be formed on the surface of the seed substrate by any method selected from the group consisting of (PVD) method and chemical vapor deposition (CVD) method.
  • the powder method include an aerosol deposition method (AD method) and a powder jet deposition method (PJD method).
  • Specific examples of the solution method include a liquid phase precipitation method, a spin coating method, and a dipping method.
  • specific examples of the physical vapor deposition (PVD) method include a sputtering method and the like.
  • examples of the chemical vapor deposition (CVD) method include a mist CVD method and a laser CVD method.
  • the fourth embodiment of the present invention is A method for producing a single crystal according to any one of the first to third embodiments of the present invention.
  • the method for forming the film on the surface of the seed substrate in the film forming step is any method selected from the group consisting of a powder method, a solution method, a physical vapor deposition (PVD) method, and a chemical vapor deposition (CVD) method. Being Is a method for producing a single crystal.
  • the fifth embodiment of the present invention provides: A method for producing a single crystal according to the fourth embodiment of the present invention, comprising:
  • the powder method is any method selected from the group consisting of an aerosol deposition method (AD method) and a powder jet deposition method (PJD method), and the solution method includes a liquid phase precipitation method, a spin coating method, and Any method selected from the group consisting of dipping methods, the physical vapor deposition (PVD) method is a sputtering method, and the chemical vapor deposition (CVD) method is any one selected from the group consisting of a mist CVD method and a laser CVD method That way, Is a method for producing a single crystal.
  • the powder method is any method selected from the group consisting of an aerosol deposition method (AD method) and a powder jet deposition method (PJD method)
  • the solution method includes a liquid phase precipitation method, a spin coating method, and Any method selected from the group consisting of dipping methods
  • a powder method, a solution method, a physical vapor deposition (PVD) method, and a chemical vapor deposition (CVD) are used as a method for forming the film on the surface of the seed substrate in the film forming step.
  • Any method selected from the group consisting of methods is adopted.
  • the fine crystal has good adhesion to the seed substrate and does not generate pores (micron order (that is, the size is 1 ⁇ m or more)) in the film.
  • the film can be reliably formed on the seed substrate.
  • the powder method is any method selected from the group consisting of an aerosol deposition method (AD method) and a powder jet deposition method (PJD method), and the solution method is a liquid phase precipitation method, a spin method A method selected from the group consisting of a coating method and a dipping method, wherein the physical vapor deposition (PVD) method is a sputtering method, and the chemical vapor deposition (CVD) method is a group consisting of a mist CVD method and a laser CVD method. Any method selected from the above. Note that details of each of the above film forming methods are well known to those skilled in the art, and a description thereof will be omitted in this specification.
  • the aerosol deposition method (AD method) or the powder jet deposition method (PJD method) is used as the powder method
  • compressive stress is applied to the film side and tensile stress is applied to the seed substrate side.
  • the seed substrate on which the film is formed (film formation) may be warped and / or wavy. If heat treatment (corresponding to the heating step in the method for producing a single crystal according to the present invention) is performed in such a state, lattice defects such as dislocations are easily generated in the obtained single crystal, and the quality of the obtained single crystal is deteriorated. There is a risk of doing.
  • the warping is performed in this way.
  • the obtained single crystal may be annealed to reduce lattice defects such as dislocations in the single crystal.
  • the annealing treatment may be performed in the temperature range of about 300 to 900 ° C. in the atmosphere.
  • the annealing treatment may be performed in an atmosphere in which zinc oxide (ZnO) vapor is present in the presence of zinc oxide (ZnO) powder or the like in the annealing atmosphere.
  • the warping and / or waviness of the seed substrate not only adversely affects the crystal growth in the heating step included in the single crystal manufacturing method according to the present invention as described above, but also the aerosol deposition method (AD Method) or powder jet deposition method (PJD method), the quality and thickness of the film formed on the surface of the seed substrate may be adversely affected.
  • the film forming step if there is warping and / or waviness on the seed substrate on which the film is formed on the surface using the aerosol deposition method (AD method) or the powder jet deposition method (PJD method).
  • the angle at which the powder (particles) sprayed toward the surface of the seed substrate collides with the surface of the seed substrate varies depending on the location.
  • the quality and / or thickness of the film formed on the surface of the seed substrate may be inhomogeneous.
  • warping and / or undulation of the seed substrate accompanying film formation increases, and it becomes more difficult to perform uniform film formation.
  • warping and / or waviness of the seed substrate occurs, when the powder sprayed toward the surface of the seed substrate collides with the surface of the seed substrate, the warped or wavy portion is deformed, and It will alleviate the impact.
  • it is difficult to secure the energy necessary for forming the film and as a result, the quality and / or thickness of the film formed on the surface of the seed substrate may be inhomogeneous. It goes without saying that such film quality and / or thickness heterogeneity affects the single crystal quality homogeneity obtained after the heat treatment in the next heating step.
  • warping and / or waviness of the seed substrate is not limited to crystal growth in the heating step included in the method for producing a single crystal according to the present invention, but also an aerosol deposition method (AD method) or a powder jet deposition method (The film quality and thickness uniformity formed by the film forming process using the PJD method may be adversely affected.
  • AD method aerosol deposition method
  • powder jet deposition method The film quality and thickness uniformity formed by the film forming process using the PJD method may be adversely affected.
  • the seed substrate is fixed to the pedestal, and there is no warp and / or waviness on the seed substrate. It is desirable to form a film in a state.
  • the method for heating the film in the heating step included in the method for producing a single crystal according to the present invention is not particularly limited as long as the above-described temperature increase rate can be realized.
  • an infrared lamp for example, a near infrared lamp
  • various lasers for example, a CO 2 laser, a YAG laser, an excimer laser, a semiconductor laser, etc.
  • the sixth embodiment of the present invention provides: A method for producing a single crystal according to any one of the first to fifth embodiments of the present invention,
  • the method of heating the film formed on the surface of the seed substrate in the heating step is a heating method using any heat source selected from the group consisting of an infrared lamp, a laser, and a high-frequency heating device, Is a method for producing a single crystal.
  • the method of heating the film formed on the surface of the seed substrate in the heating step includes an infrared lamp, a laser, and a high-frequency heating device. It is a heating method using any heat source selected from the group.
  • the rate of temperature rise of the film in the heating step can be reliably and easily set to 30 ° C./min or more, more preferably 300 ° C./min or more.
  • the generation of pores in the process of obtaining the single crystal in the heating step can be more reliably and easily suppressed.
  • the film formed on the surface of the seed substrate may be a film having low crystallinity (hereinafter sometimes referred to as “microcrystalline film”). More desirably, an amorphous film is even more desirable.
  • the seventh embodiment of the present invention provides: A method for producing a single crystal according to any one of the first to sixth embodiments of the present invention,
  • the film formed in the film forming step is amorphous; Is a method for producing a single crystal.
  • the film formed in the film forming step is amorphous.
  • the crystallinity of the film formed on the surface of the seed substrate in the film forming step included in the single crystal manufacturing method according to the present invention is calculated by, for example, performing XRD measurement of the film and calculating the crystallite size by the WPPD method. Can be evaluated.
  • a crystallite measured using an enclosed tube X-ray diffractometer (D8 ADVANCE manufactured by Bruker AXS) under the following conditions: The size was 10.85 nm.
  • Tube current 40 mA
  • Step width 0.02 ° ⁇
  • Measurement range: 2 ⁇ 20 ⁇ 70 ° ⁇
  • a film having a crystallite size calculated by the WPPD method exceeding 50 nm is defined as a polycrystalline film, and a film having a crystallite size of 50 nm or less is defined as a microcrystalline film.
  • amorphous refers to a property in which a diffraction peak due to a crystal does not appear in in-plane rocking curve (XRC) measurement.
  • the method for forming an amorphous film on the surface of the seed substrate in the film forming step included in the single crystal manufacturing method according to the above embodiment has good adhesion to the seed substrate and is a film.
  • a dense film on the seed substrate that does not generate pores (micron order (that is, a size of 1 ⁇ m or more)) inside.
  • an amorphous film is formed in the film forming step included in the single crystal manufacturing method according to the present embodiment, for example, powder is sprayed toward the target substrate or the like to And depositing or coating the main component and / or precursor on the surface of a substrate or the like using a powder method for solidifying the powder and a solution containing the main component and / or precursor of the membrane.
  • the amorphous film can be formed on the surface of the seed substrate by any method selected from the group consisting of a solution method, a physical vapor deposition (PVD) method, and a chemical vapor deposition (CVD) method.
  • specific examples of the powder method include an aerosol deposition method (AD method) and a powder jet deposition method (PJD method).
  • Specific examples of the solution method include a liquid phase precipitation method, a spin coating method, and a dipping method.
  • specific examples of the physical vapor deposition (PVD) method include a sputtering method and the like.
  • examples of the chemical vapor deposition (CVD) method include a mist CVD method and a laser CVD method.
  • the main component of the film formed on the surface of the seed substrate in the film forming step included in the single crystal manufacturing method according to the present invention is not particularly limited as long as the target single crystal can be manufactured.
  • a single crystal mainly composed of oxide or nitride eg, zinc oxide (ZnO), titanium oxide (TiO 2 ), gallium nitride (GaN), etc.
  • ZnO zinc oxide
  • TiO 2 titanium oxide
  • GaN gallium nitride
  • the method for producing a single crystal according to the present invention an appropriate temperature gradient is generated in the film by heating a film having a thickness of a predetermined value or less as described above at a heating rate of a predetermined value or more.
  • the generation of pores in the obtained crystal film can be suppressed. That is, the method for producing a single crystal according to the present invention can be particularly suitably applied to obtain a single crystal mainly composed of oxide or nitride.
  • the main component of the film formed on the surface of the seed substrate in the film forming step included in the single crystal manufacturing method according to the present invention and the main component of the single crystal manufactured by the single crystal manufacturing method according to the present invention May be the same or different.
  • a film formed in the film forming step is made amorphous as described above, for example, a film containing the same substance as the main component of the target single crystal as a main component (for example, When formed (by any of the various methods described above), the formed film may crystallize.
  • a film is formed with a precursor having a composition different from that of the final single crystal in the film formation step, and the precursor is chemically changed into a main component of the single crystal in a subsequent heating step.
  • the target single crystal By crystallizing, the target single crystal can be obtained.
  • Specific examples of such precursors include zinc oxynitride (ZnON).
  • Zinc oxide (ZnO) crystallizes when deposited by sputtering. However, by introducing nitrogen during film formation by sputtering, generation of zinc oxide (ZnO) crystal nuclei is suppressed, and a zinc oxynitride (ZnON) film having a low crystal nucleus density can be obtained (for example, Patent Document 6). See). Then, the target single crystal of zinc oxide (ZnO) can be obtained by heat treatment in the heating step.
  • the eighth embodiment of the present invention provides: A method for producing a single crystal according to any one of the first to seventh embodiments of the present invention,
  • the main component of the film is any one material selected from the group consisting of oxides and nitrides, and precursors thereof; Is a method for producing a single crystal.
  • oxide and nitride which can be used as the main component of the film formed on the surface of the seed substrate in the single crystal manufacturing method according to the present embodiment, as described above, zinc oxide is used as described above.
  • ZnO zinc oxide
  • TiO 2 titanium oxide
  • GaN gallium nitride
  • the ninth embodiment of the present invention provides: A method for producing a single crystal according to the eighth embodiment of the present invention, comprising: The oxide is zinc oxide (ZnO) and titanium oxide (TiO 2 ), and the nitride is gallium nitride (GaN); Is a method for producing a single crystal.
  • an upper limit is set for the maximum temperature reached in the heating step, or an upper limit is set for the holding time at the maximum temperature.
  • it is necessary to set these upper limits with due consideration of the melting point of the substance used as the main component of the film, the thickness of the film, and the like.
  • a substrate having a single crystal layer formed on the surface may be used as a seed substrate used in the method for producing a single crystal according to the present invention.
  • the single crystal layer may be formed on the substrate by, for example, a thin film manufacturing method.
  • the film containing the single crystal raw material manufactured by the single crystal manufacturing method according to the present invention is formed on the surface of the single crystal layer.
  • the tenth embodiment of the present invention provides: A method for producing a single crystal according to any one of the first to ninth embodiments of the present invention,
  • the seed substrate is a substrate on which a single crystal layer is formed; and the film is formed on the surface of the single crystal layer; Is a method for producing a single crystal.
  • a substrate having a single crystal layer formed on the surface is used as a seed substrate, and the single crystal produced by the method for producing a single crystal according to the present invention is used.
  • a film containing the raw material is formed on the surface of the single crystal layer.
  • the substrate is not particularly limited as long as the single crystal layer can be formed on the surface and does not adversely affect the single crystal manufacturing method according to the present invention.
  • the method for forming a single crystal layer as a seed substrate on the surface of the substrate is not particularly limited, but specific examples include, for example, a solid phase epitaxial growth method, a vapor phase epitaxial growth method, a liquid phase epitaxial method, and the like. Can do.
  • Specific examples of the vapor phase epitaxial growth method include, for example, molecular beam epitaxy (MBE) method, radical source molecular beam epitaxy (RS-MBE) method, metal organic vapor phase epitaxy (MOCVD) method, pulsed laser deposition (PLD) Method, sputtering method and the like.
  • Specific examples of the liquid phase epitaxial growth method include a liquid phase precipitation method, a flux method, a hydrothermal method, a spin coating method, a dipping method, and the like.
  • a single crystal layer of zinc oxide (ZnO) is formed on the surface of a substrate made of sapphire by the MBE method.
  • a film containing zinc oxide (ZnO) raw material powder is formed on the surface of the single crystal layer of the seed substrate by an AD method in the film formation step.
  • a process for manufacturing a single crystal of zinc oxide (ZnO) by heating the film under conditions can be given.
  • the production of a single crystal of zinc oxide (ZnO) by the single crystal manufacturing method according to the above embodiment corresponds to heteroepitaxial growth, but as described above, in the seed substrate, oxidation is performed.
  • the zinc (ZnO) single crystal layer being formed on the surface, homoepitaxial growth is achieved, and a zinc oxide (ZnO) single crystal having better crystallinity can be obtained.
  • a film containing the raw material of the single crystal to be manufactured by the method is formed (film formation) on the surface of the seed substrate, and in the heating step
  • the film formed on the surface of the seed substrate is subjected to a heat treatment under a predetermined condition to obtain a target single crystal.
  • a heat treatment under a predetermined condition to obtain a target single crystal.
  • a metal or ceramic jig is used to suppress warping and / or waviness of the seed substrate. It is preferable to perform the heat treatment in the state where it is applied.
  • the eleventh embodiment of the present invention is A method for producing a single crystal according to any one of the first to tenth embodiments of the present invention, In the heating step, heating the film in a state where an evaluation index corresponding to warpage and / or waviness of the seed substrate is equal to or lower than a predetermined upper limit value, Is a method for producing a single crystal.
  • the evaluation index corresponding to warpage and / or waviness of the seed substrate is equal to or lower than a predetermined upper limit value. Heat the membrane.
  • the evaluation index corresponding to the warpage and / or waviness of the seed substrate is, for example, the warpage of the seed substrate that can achieve the quality required in the use of the single crystal manufactured by the single crystal manufacturing method according to this embodiment and / or Or it can select suitably according to the magnitude
  • an evaluation index for example, various surface property parameters measured by a surface shape / roughness measuring device or the like can be employed.
  • the upper limit value determined in advance for such an evaluation index is also, for example, warpage and / or undulation of the seed substrate that can achieve the quality required in the use of the single crystal manufactured by the single crystal manufacturing method according to the present embodiment. It can be determined as appropriate according to the size and the period.
  • the predetermined upper limit value is, for example, the frequency of lattice defects that can be tolerated in the use of the single crystal manufactured by the single crystal manufacturing method according to the present embodiment (hereinafter referred to as “defect density”). It is possible to define the maximum value of the evaluation index corresponding to the warpage and / or undulation of the seed substrate.
  • the maximum height (Pt) of the cross-sectional curve can be adopted among various surface property parameters measured by a surface shape / roughness measuring machine or the like.
  • the present inventor has found that the surface of the seed substrate in a state where the maximum value (Pt) of the cross-sectional curve as an evaluation index corresponding to warpage and / or waviness of the seed substrate is 5 ⁇ m or less in the heating step It has been found that by heating the film formed above, the generation of lattice defects such as dislocations in the resulting single crystal can be effectively reduced.
  • the first modification of the eleventh embodiment of the present invention is A method for producing a single crystal according to the eleventh embodiment of the present invention, comprising:
  • the evaluation index is a maximum cross-sectional curve height (Pt), and the upper limit is 5 ⁇ m, Is a method for producing a single crystal.
  • Examples include a method of correcting a seed substrate in which warpage and / or undulation has already occurred at a time before the heating step included in the method for producing a single crystal according to the invention so that the warpage and / or undulation is suppressed. it can.
  • a jig is used to make the seed substrate flat (for example, flat).
  • a method of bonding a seed substrate can be given.
  • Examples of the method for bonding the seed substrate to the flat surface include indirect bonding and direct bonding.
  • indirect bonding for example, a method of applying and bonding an adhesive and / or a binder to at least one of a bonding surface of a seed substrate and a bonding surface of a flat surface by a coating method such as a spin coating method And a method of attaching a seed substrate to a flat surface by ceramics and / or metal paste (for example, baking (brazing) using a metal containing a noble metal such as platinum (Pt)).
  • a bonding surface of a seed substrate and a bonding surface of a flat surface is activated by irradiation with an ion beam such as an argon (Ar) beam, and the bonding surface of the seed substrate is flat.
  • an ion beam such as an argon (Ar) beam
  • a method in which the bonding surface is pressed in close contact with pressure and a method in which the bonding surface of the seed substrate is bonded to a flat bonding surface and heated can be used.
  • the seed substrate is flattened using a vacuum chuck, an electrostatic chuck, or the like.
  • a method of adsorbing on a flat surface for example, the surface of a flat pedestal
  • tool used in the said method the joint surface of the flat surface to which a seed substrate is adhere
  • the intermediate agent for example, an adhesive agent, binder, ceramics, metal used for indirect joining of a seed substrate and a flat surface
  • the intermediate agent for example, an adhesive agent, binder, ceramics, metal used for indirect joining of a seed substrate and a flat surface
  • the material is made of a material to be obtained. Specific examples of such materials include metals and ceramics.
  • the second modification of the eleventh embodiment of the present invention is: A method for producing a single crystal according to the eleventh embodiment (including the first modification of the eleventh embodiment) of the present invention, Pressing the seed substrate against a flat surface using a jig, applying a tension in a direction parallel to the main surface of the seed substrate using a jig, and bonding the seed substrate to a flat surface That the evaluation index is less than or equal to the upper limit value by adsorbing the seed substrate to a flat surface using a vacuum chuck and / or an electrostatic chuck, Is a method for producing a single crystal.
  • the single crystal manufacturing method according to the present invention is used. It is also effective to prevent the seed substrate from warping and / or waviness in the film forming step included in the step.
  • the third modification of the eleventh embodiment of the present invention is A method for producing a single crystal according to the eleventh embodiment (including the first modification of the eleventh embodiment) of the present invention, Forming a film on the surface of the seed substrate bonded to the holding substrate in the film forming step; Is a method for producing a single crystal.
  • a film is formed on the surface of the seed substrate bonded to the holding substrate in the film forming step.
  • the seed substrate is warped due to the influence of stress, heat, etc. acting on the seed substrate and / or the film formed on the surface of the seed substrate. It is possible to reduce the possibility of swells.
  • the specific method for bonding the seed substrate and the holding substrate is, for example, stress, heat, etc. acting on the seed substrate and / or a film formed on the surface of the seed substrate in the film forming step and the heating step.
  • Specific examples of the method for bonding the seed substrate and the holding substrate include indirect bonding and direct bonding.
  • indirect bonding for example, a method of applying and bonding an adhesive and / or a binder to at least one of the bonding surface of the seed substrate and the bonding surface of the holding substrate by a coating method such as a spin coating method
  • a coating method such as a spin coating method
  • examples include a method of attaching a seed substrate to a holding substrate by ceramics and / or metal paste (for example, baking (brazing) using a metal containing a noble metal such as platinum (Pt)).
  • the direct bonding for example, at least one of the bonding surface of the seed substrate and the bonding surface of the holding substrate is activated by irradiation with an ion beam such as an argon (Ar) beam, and the bonding surface of the seed substrate and the holding substrate are activated. And a method in which the bonding surface of the seed substrate is pressed and a method of heating the bonding surface of the seed substrate and the bonding surface of the holding substrate (solid phase bonding).
  • the bonding surface of the holding substrate to which the seed substrate is bonded, and the intermediate agent for example, adhesive, binder, ceramics, metal paste, etc.
  • the intermediate agent for example, adhesive, binder, ceramics, metal paste, etc.
  • the holding substrate bonded to the seed substrate has rigidity and / or heat resistance equal to or higher than a predetermined lower limit value.
  • the predetermined lower limit value of the rigidity and / or heat resistance of the holding substrate is, for example, stress, heat, etc. acting on the seed substrate and / or the film formed on the surface of the seed substrate in the film forming step. It can be determined appropriately according to the degree.
  • the single crystal manufacturing method according to the present invention is a single crystal manufacturing method by an epitaxial growth method, but the main component of the single crystal manufactured by the single crystal manufacturing method and the single crystal layer constituting the seed substrate or the seed substrate are used.
  • the main component may be the same or different.
  • the single crystal manufacturing method according to the present invention may be a homoepitaxial growth method or a heteroepitaxial growth method.
  • the single crystal production method according to the present invention is a homoepitaxial growth method
  • the main component of the single crystal produced by the single crystal production method is the same as the main component of the seed substrate or the single crystal layer constituting the seed substrate. .
  • the seed substrate or the seed substrate is configured.
  • the main component of the single crystal layer is also zinc oxide (ZnO), titanium oxide (TiO 2 ), or gallium nitride (GaN), respectively.
  • the single crystal manufacturing method according to the present invention is a heteroepitaxial growth method, the main component of the single crystal produced by the single crystal manufacturing method is different from the main component of the seed substrate or the single crystal layer constituting the seed substrate. .
  • the seed substrate or the seed substrate is configured.
  • the main component of the single crystal layer is a substance that is not zinc oxide (ZnO), a substance that is not titanium oxide (TiO 2 ), or a substance that is not gallium nitride (GaN).
  • a substance that is not zinc oxide (ZnO), titanium oxide (TiO 2 ), or gallium nitride (GaN), which can be used as a main component of the seed substrate or the single crystal layer constituting the seed substrate For example, sapphire can be mentioned.
  • the twelfth embodiment of the present invention is A method for producing a single crystal according to any one of the first to eleventh embodiments of the present invention
  • the main component of the seed substrate or the single crystal layer is any one material selected from the group consisting of zinc oxide (ZnO), gallium nitride (GaN), titanium oxide (TiO 2 ), and sapphire, Is a method for producing a single crystal.
  • the main components of the seed substrate or the single crystal layer are zinc oxide (ZnO), gallium nitride (GaN), titanium oxide (TiO 2 ), and Any one material selected from the group consisting of sapphire. Therefore, the main component of the film formed on the surface of the seed substrate and the main component of the seed substrate or the single crystal layer constituting the seed substrate are both zinc oxide (ZnO) or titanium oxide (TiO 2 ). Or gallium nitride (GaN), the single crystal manufacturing method according to this embodiment is a homoepitaxial growth method.
  • the single crystal manufacturing method according to this embodiment This is a heteroepitaxial growth method.
  • the main component of the single crystal produced by the method for producing a single crystal according to the present invention may be a so-called “mixed crystal”. That is, the main component of the single crystal produced by the method for producing a single crystal according to the present invention may be, for example, a mixed crystal containing two or more kinds of metal elements, or a mixed crystal containing two or more kinds of nonmetallic elements. It may be a mixed crystal containing two or more kinds of metal elements and two or more kinds of nonmetal elements.
  • control of the band gap in the single crystal produced by the single crystal manufacturing method according to the present invention is performed. For example, when the single crystal is used as an LED substrate, Desired characteristics such as setting the emission wavelength of the LED to a desired wavelength can be imparted to the single crystal.
  • the main component of the seed substrate or the single crystal layer constituting the seed substrate may be a mixed crystal. That is, the seed substrate used in the method for producing a single crystal according to the present invention or the main component of the single crystal layer constituting the seed substrate may also be a so-called “mixed crystal”. That is, the main component of the seed substrate or the single crystal layer constituting the seed substrate used in the single crystal manufacturing method according to the present invention may be, for example, a mixed crystal containing two or more kinds of metal elements. A mixed crystal containing the above nonmetallic elements may be used, or a mixed crystal containing two or more kinds of metallic elements and two or more kinds of nonmetallic elements may be used.
  • the main components of the seed substrate or the single crystal layer constituting the seed substrate are, for example, magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe).
  • MgO magnesium oxide
  • CdO cadmium oxide
  • ZnS zinc sulfide
  • ZnTe zinc telluride
  • ZnO zinc oxide
  • AlN aluminum nitride
  • InN indium nitride
  • gallium nitride It may be a mixed crystal with (GaN).
  • the thirteenth embodiment of the present invention provides: A method for producing a single crystal according to any one of the first to eleventh embodiments of the present invention, One or more selected from the group consisting of magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe) as the main component of the seed substrate or the single crystal layer and zinc oxide
  • MgO magnesium oxide
  • CdO cadmium oxide
  • ZnS zinc sulfide
  • ZnTe zinc telluride
  • ZnTe zinc telluride
  • a mixed crystal of (ZnO) or a mixed crystal of at least one selected from the group consisting of aluminum nitride (AlN) and indium nitride (InN) and gallium nitride (GaN) Is a method for producing a single crystal.
  • the main component of the seed substrate or the single crystal layer is magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and tellurium.
  • MgO magnesium oxide
  • CdO cadmium oxide
  • ZnS zinc sulfide
  • tellurium One or more selected from the group consisting of zinc halide (ZnTe) and zinc oxide (ZnO), or one or more selected from the group consisting of aluminum nitride (AlN) and indium nitride (InN) and gallium nitride ( Mixed crystal with GaN).
  • the main component of a single crystal produced by the method for producing a single crystal according to the present invention is a mixed crystal and the band gap in the single crystal is to be controlled, the expected result of mixed crystallization
  • the crystallinity of the single crystal can be enhanced while achieving the effects (for example, imparting desired characteristics).
  • the film formed on the surface of the seed substrate is not limited to the above-mentioned various main components, as long as it does not adversely affect the properties of the resulting single crystal.
  • Impurities dopants may be contained.
  • a component constituting the film for example, aluminum (Al), gallium (Ga), indium (In), nitrogen (N), boron (B), phosphorus (P), arsenic (As), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), carbon (C), silicon (Si), sulfur (S), lithium (Li), sodium (Na), potassium (K), magnesium Oxidize at least one element selected from the group consisting of (Mg), cadmium (Cd), selenium (Se), tellurium (Te), silver (Ag), niobium (Nb), and copper (Cu).
  • a material doped with a main component such as zinc (ZnO) may be used.
  • the fourteenth embodiment of the present invention is A method for producing a single crystal according to any one of the first to thirteenth embodiments of the present invention, comprising:
  • the film is made of aluminum (Al), gallium (Ga), indium (In), nitrogen (N), boron (B), phosphorus (P), arsenic (As), fluorine (F), chlorine (Cl), bromine.
  • the film is made of aluminum (Al), gallium (Ga), indium (In), nitrogen (N), boron (B), phosphorus (P).
  • the electric characteristics, piezoelectric / electrostrictive characteristics, and the like of the resulting single crystal can be adjusted to a desired level.
  • the single crystal manufacturing method according to the present embodiment when a substance containing aluminum (Al) or gallium (Ga) is used as the main component of the film formed on the surface of the seed substrate, aluminum (Al)
  • gallium (Ga) cannot be contained as an impurity (dopant).
  • impurities are mixed, the crystallinity and / or defect density of a single crystal may be adversely affected.
  • impurities dopants
  • epitaxial growth is inhibited by adding impurities (dopants) in an amount exceeding the solid solution limit with respect to the main component of the film, such as zinc oxide (ZnO). This is undesirable because it adversely affects the crystallinity and / or defect density of the single crystal.
  • the main component of the single crystal produced by the method for producing a single crystal according to the present invention may be a so-called “mixed crystal”. That is, the main component of the single crystal produced by the method for producing a single crystal according to the present invention may be, for example, a mixed crystal containing two or more kinds of metal elements, or a mixed crystal containing two or more kinds of nonmetallic elements. It may be a mixed crystal containing two or more kinds of metal elements and two or more kinds of nonmetal elements.
  • control of the band gap in the single crystal produced by the single crystal manufacturing method according to the present invention is performed.
  • the single crystal when used as an LED substrate, Desired characteristics such as setting the emission wavelength of the LED to a desired wavelength can be imparted to the single crystal.
  • the main component of the single crystal is, for example, one or more selected from the group consisting of magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe).
  • the fifteenth embodiment of the present invention provides: A method for producing a single crystal according to any one of the first to fourteenth embodiments of the present invention, comprising:
  • the film is a mixed crystal of zinc oxide (ZnO) and at least one selected from the group consisting of magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe) and / or Or a mixture, or a mixed crystal and / or a mixture of at least one selected from the group consisting of aluminum nitride (AlN) and indium nitride (InN) and gallium nitride (GaN), Is a method for producing a single crystal.
  • AlN aluminum nitride
  • InN indium nitride
  • GaN gallium nitride
  • the film is made of magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe).
  • MgO magnesium oxide
  • CdO cadmium oxide
  • ZnS zinc sulfide
  • ZnTe zinc telluride
  • AlN aluminum nitride
  • InN indium nitride
  • GaN gallium nitride
  • MgO magnesium oxide
  • CdO cadmium oxide
  • ZnS zinc sulfide
  • ZnTe zinc telluride
  • a mixed crystal of zinc oxide (ZnO) or a mixed crystal of gallium nitride (GaN) with at least one selected from the group consisting of aluminum nitride (AlN) and indium nitride (InN) can be produced.
  • a mixed crystal As described above, by forming a mixed crystal in this way, for example, control of a band gap in a single crystal produced by the method for producing a single crystal according to the present invention is performed.
  • the single crystal is used as an LED substrate.
  • desired characteristics can be imparted to the single crystal, such as setting the emission wavelength of the LED to a desired wavelength.
  • a mixed crystal of magnesium oxide (MgO) and zinc oxide (ZnO) which is an example of a mixed crystal produced by the single crystal manufacturing method according to this embodiment, is represented by the composition formula Mg x Zn 1-x O. Can do.
  • x represents the ratio of magnesium (Mg) in the metal element contained in the mixed crystal, and can be configured to satisfy, for example, 0 ⁇ x ⁇ 0.4.
  • the film thickness that is the thickness in the direction orthogonal to the surface of the seed substrate is 100 ⁇ m or less.
  • the heating step of heating the film formed on the surface of the seed substrate to obtain a single crystal the film is heated from the side of the seed substrate, High-quality single crystal with few pores not only in the material system that makes it easy to obtain a raw material melt, but also in the material system that makes it difficult to obtain a raw material melt Can be produced with high productivity.
  • the thickness of the obtained single crystal film is 100 ⁇ m or less, more preferably 30 ⁇ m or less. Therefore, for example, when a single crystal having a larger thickness such as a single crystal wafer is to be manufactured, it is necessary to repeatedly execute the single crystal manufacturing method according to the present invention over a plurality of cycles.
  • the sixteenth embodiment of the present invention is Obtaining a single crystal by repeatedly executing the method for producing a single crystal according to any one of the first to fifteenth embodiments of the present invention; Is a method for producing a single crystal.
  • the single crystal manufacturing method according to the present invention including the various embodiments described so far is repeatedly executed over a plurality of cycles.
  • a single crystal having a desired thickness can be obtained.
  • the seventeenth embodiment of the present invention is Obtained by the method for producing a single crystal according to any one of the first to fourteenth embodiments and the sixteenth embodiment of the present invention, A zinc oxide (ZnO) single crystal characterized by
  • the thickness of the obtained single crystal film is generally 100 ⁇ m or less, more preferably 30 ⁇ m or less. However, depending on the application, a single crystal having a thickness exceeding 30 ⁇ m may be desirable.
  • the eighteenth embodiment of the present invention provides: A zinc oxide (ZnO) single crystal according to the seventeenth embodiment of the present invention, A crystal thickness that is a thickness of the crystal in a direction orthogonal to the surface of the seed substrate of the film formed in the film forming step exceeds 30 ⁇ m; A zinc oxide (ZnO) single crystal characterized by
  • a single crystal having a thickness exceeding 100 ⁇ m may be desirable.
  • the thickness of the obtained single crystal film is generally 100 ⁇ m or less. Therefore, for example, when a single crystal having a larger thickness such as a single crystal wafer is to be manufactured, it is necessary to repeatedly execute the single crystal manufacturing method according to the present invention over a plurality of cycles.
  • the nineteenth embodiment of the present invention is A zinc oxide (ZnO) single crystal according to the eighteenth embodiment of the present invention, It is obtained by the single crystal manufacturing method according to claim 16, and a crystal thickness that is a thickness of the crystal in a direction perpendicular to the surface of the seed substrate of the film formed in the film forming step exceeds 100 ⁇ m.
  • a zinc oxide (ZnO) single crystal characterized by
  • the film formed on the surface of the seed substrate does not adversely affect the characteristics of the resulting single crystal.
  • impurities dopants
  • a component constituting the film for example, aluminum (Al), gallium (Ga), indium (In), nitrogen (N), boron (B), phosphorus (P), arsenic (As), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), carbon (C), silicon (Si), sulfur (S), lithium (Li), sodium (Na), potassium (K), magnesium Oxidize at least one element selected from the group consisting of (Mg), cadmium (Cd), selenium (Se), tellurium (Te), silver (Ag), niobium (Nb), and copper (Cu).
  • a material doped with a main component such as zinc (ZnO) may be used. By containing these dopants, for example, desired characteristics such as n-type conversion, p-type conversion, or band gap control can be imparted to the single crystal.
  • Al aluminum (Al), gallium (Ga), indium (In), boron (B), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and n-type dopants Silicon (Si) is desirable, and aluminum (Al), gallium (Ga), and indium (In) are particularly desirable.
  • the content of these impurities (dopants) is preferably 0.02 at% or more, more preferably 0.1 at% or more. When the content of these impurities (dopants) is less than 0.02 at%, it is difficult to obtain the desired desired characteristics such as high conductivity (low electrical resistance), for example. Absent.
  • the twentieth embodiment of the present invention provides: A zinc oxide (ZnO) single crystal according to any one of the seventeenth to nineteenth embodiments of the present invention, Containing at least one element selected from the group consisting of aluminum (Al), gallium (Ga), and indium (In) as impurities, and the impurity content is 0.02 at% or more.
  • a zinc oxide (ZnO) single crystal characterized by
  • the twenty-first embodiment of the present invention provides A zinc oxide (ZnO) single crystal according to the twentieth embodiment of the present invention,
  • the impurity content is 0.1 at% or more,
  • examples of the characteristics that can be achieved by adding an n-type dopant to the main component constituting the single crystal according to the present invention include high conductivity (low electrical resistance) and the like. Can do.
  • a zinc oxide single crystal is used as a substrate of an electronic device using a pn junction such as an LED
  • the result is obtained when the single crystal itself is used as an electrode (cathode) on the n-type layer side.
  • the resistivity of the obtained single crystal is desirably 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
  • the twenty-second embodiment of the present invention is A zinc oxide (ZnO) single crystal according to any one of the seventeenth to twenty-first embodiments of the present invention, Resistivity is 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less, A zinc oxide (ZnO) single crystal characterized by
  • the main component of the single crystal produced by the method for producing a single crystal according to the present invention may be a so-called “mixed crystal”.
  • the single crystal produced by the method for producing a single crystal according to the present invention is mixed to control the band gap in the single crystal, for example, and the single crystal is used as the substrate of the LED, for example.
  • desired characteristics can be imparted to the single crystal, such as setting the emission wavelength of the LED to a desired wavelength.
  • the main component of the single crystal is, for example, one or more selected from the group consisting of magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe).
  • the twenty-third embodiment of the present invention provides: Obtained by the method for producing a single crystal according to any one of the fifteenth and sixteenth embodiments of the present invention, and magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and One or more selected from the group consisting of one or more selected from the group consisting of zinc telluride (ZnTe) and zinc oxide (ZnO), or the group consisting of aluminum nitride (AlN) and indium nitride (InN) And a mixed crystal of gallium nitride (GaN), Is a single crystal characterized by
  • the single crystal according to this embodiment can be obtained by the method for producing a single crystal according to any one of the fifteenth and sixteenth embodiments of the present invention. That is, the single crystal according to this embodiment includes at least one selected from the group consisting of magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe) and zinc oxide (ZnO). ) Or a mixed crystal and / or mixture of at least one selected from the group consisting of aluminum nitride (AlN) and indium nitride (InN) and gallium nitride (GaN).
  • MgO magnesium oxide
  • CdO cadmium oxide
  • ZnS zinc sulfide
  • ZnTe zinc telluride
  • ZnO zinc oxide
  • AlN aluminum nitride
  • InN indium nitride
  • GaN gallium nitride
  • a film containing the film on the surface of the seed substrate can be obtained by forming a film containing the film on the surface of the seed substrate and heating the film under predetermined conditions. Moreover, a single crystal having a desired thickness can be obtained by repeatedly executing such a single crystal manufacturing method over a plurality of cycles as necessary.
  • the single crystal according to this embodiment is one or more selected from the group consisting of magnesium oxide (MgO), cadmium oxide (CdO), zinc sulfide (ZnS), and zinc telluride (ZnTe). And zinc oxide (ZnO), or a mixed crystal of gallium nitride (GaN) with at least one selected from the group consisting of aluminum nitride (AlN) and indium nitride (InN).
  • the band gap of the single crystal is controlled.
  • the emission wavelength of the LED is set to a desired wavelength. The desired characteristics can be achieved.
  • a mixed crystal of magnesium oxide (MgO) and zinc oxide (ZnO), which is an example of a single crystal according to this embodiment, can be represented by a composition formula Mg x Zn 1-x O.
  • x represents the ratio of magnesium (Mg) in the metal element contained in the mixed crystal, and can be configured to satisfy, for example, 0 ⁇ x ⁇ 0.4.
  • the powder thus wet-mixed was fired in air at 1400 ° C. for 5 hours to synthesize zinc oxide (ZnO) powder in which aluminum (Al) was dissolved.
  • the synthetic powder thus obtained was wet-ground for 5 hours in a pot mill using zirconia balls so that the volume standard D50 was 2.6 ⁇ m.
  • Zinc oxide (ZnO) in which 0.2 at% of aluminum (Al) was obtained as described above was obtained in Experimental Examples 01 and 02, Experimental Examples 04 to 07, and Experimental Examples 09 to 13. Used as film forming raw material powder (film forming powder).
  • ZnO zinc oxide
  • D50 gallium nitride
  • FIG. 1 is a schematic diagram showing the configuration of a film forming apparatus used in the single crystal manufacturing method according to one embodiment of the present invention as described above.
  • the film forming apparatus 20 includes an aerosol generating unit 22 that generates an aerosol of a raw material powder containing a raw material component, and a film forming unit 30 that sprays the film forming powder onto the seed substrate 21 to form a film containing the raw material component. ing.
  • the aerosol generating unit 22 contains the film forming powder 12 and receives the supply of the carrier gas 11 from a gas cylinder (not shown) to generate an aerosol, and supplies the generated aerosol to the film forming unit 30.
  • a raw material supply pipe 24, an aerosol generation chamber 23, and a vibrator 25 for applying vibration to the aerosol therein at a frequency of 10 to 100 Hz are provided.
  • the film forming unit 30 includes a film forming chamber 32 that injects aerosol onto the seed substrate 21, a seed substrate holder 34 that is disposed inside the film forming chamber 32 and fixes the seed substrate 21, and the seed substrate holder 34 is connected to the X axis ⁇ And an XY stage 33 that moves in the Y-axis direction.
  • the film forming unit 30 includes a spray nozzle 36 that has a slit 37 formed at the tip thereof and sprays aerosol onto the seed substrate 21, and a vacuum pump 38 that decompresses the film forming chamber 32.
  • nitrogen (N 2 ) gas is flowed as the carrier gas 11 at a flow rate of 6 L / min, the pressure in the aerosol generation chamber 23 is 50 to 70 kPa, and the pressure in the film forming chamber 32 is increased.
  • the opening size of the slit 37 provided in the spray nozzle 36 for film forming powder was 10 mm ⁇ 0.8 mm.
  • the opening size of the slit 37 was set to 10 mm ⁇ 0.4 mm.
  • scanning was performed simultaneously with film formation at a scanning distance of 12 mm at the scanning speed and the number of scans listed in Table 1.
  • the thickness of the various films thus obtained is such that a film forming part and a non-film forming part are formed on the substrate by masking a part of the substrate at the time of film formation.
  • the thickness of the film was determined by measuring the level difference from the part.
  • a small shape roughness measuring machine manufactured by Taylor-Hobson, “Form Talysurf plus” was used.
  • the thicknesses of various films according to each experimental example are also listed in Table 1.
  • FIG. 2 is a schematic diagram showing the configuration of the heating device used in the single crystal manufacturing method according to one embodiment of the present invention as described above.
  • a near-infrared lamp 206 is used as a light source for light heating. Since the various films have a low near-infrared absorption coefficient, a platinum plate 203 is disposed on the surface opposite to the surface on which the film 201 of the seed substrate 202 is deposited, and the surface on which the film 201 of the seed substrate 202 is deposited.
  • the film 201 was heated from the seed substrate 202 side by irradiating near infrared rays from the same side and causing the platinum plate 203 to absorb the near infrared rays.
  • the seed substrate 202 and the platinum plate 203 were placed on a quartz pedestal 204, and the temperature of the film 201 was measured by a thermocouple 205.
  • the heating temperature, the heating rate, and the holding time are as listed in Table 1.
  • the film was heated from the seed substrate side by irradiating near infrared rays from the side opposite to the surface on which the film of the seed substrate 202 was deposited.
  • an electric furnace was employed as the heating means, and the temperature of the entire heating chamber was heated by the electric furnace. In any sample, no change in the film thickness was observed before and after the heating step.
  • a single crystal having a thickness of 250 ⁇ m in the direction perpendicular to the surface of the seed substrate was formed by repeating the film forming step and the heating step 100 times.
  • In-plane rocking curve (XRC) measurement A multi-functional high-resolution X-ray diffractometer (Bulker AXS Co., Ltd., D8 DISCOVER) is used for the C-plane of various evaluation samples that have undergone the above heating step. In-plane rocking curve (XRC) measurements were made using under conditions. When the (100) peak was detected, it was judged that a dense single crystal film was obtained satisfactorily.
  • Tube voltage 40kV ⁇ Tube current: 40 mA ⁇ Anti-scattering slit: 3 ° ⁇ Step width: 0.001 ° ⁇ Scanning speed: 0.5 seconds / step ⁇ Incident angle: 1 °
  • ⁇ represents resistivity [ ⁇ ⁇ cm]
  • F represents resistivity correction coefficient
  • t represents film thickness [cm]
  • R represents resistance [ ⁇ ].
  • the resistivity correction coefficient F was calculated using the formula described in JIS K 7194.
  • the thickness of the film deposited on the seed substrate exceeds 100 ⁇ m (Experimental Example 11), and the heating rate in the heating step is less than 30 ° C./min. (Experimental example 12)
  • the entire film is heated gently and uniformly in the heating step (Experimental example 13)
  • a large number of pores are generated in the film, and a dense single crystal film is obtained. It was confirmed that it was not possible. That is, when the requirements for the single crystal manufacturing method according to the present invention are not satisfied, it is difficult to obtain a good single crystal film.
  • aluminum (Al) as an impurity was uniformly contained in the film in a concentration range of 0.1 to 0.3 at%. A single crystal having a very low resistivity of 10 ⁇ 3 ⁇ ⁇ cm or less could be obtained.
  • the thickness of the film deposited on the seed substrate is 100 ⁇ m or less
  • the heating rate in the heating step is 30 ° C./min or more
  • the film is heated from the seed substrate side in the heating step.
  • the present invention is such that the thickness of the film deposited on the seed substrate is 30 ⁇ m or less, the heating rate in the heating step is 300 ° C./min or more, and the film is heated from the seed substrate side in the heating step.
  • the more preferable requirements of the single crystal manufacturing method according to the above are satisfied, it has extremely good quality from the viewpoints of pore suppression in the film, promotion of single crystallization, and homogeneous distribution of impurities (dopants) Single crystal films could be obtained (see, for example, Experimental Examples 01 to 04 and Experimental Examples 08 to 10).
  • the amorphous film is formed in the film forming step, thereby facilitating the single crystallization in the heating step, so that the raw material melt can be easily obtained as well as the raw material melt. This was carried out for the purpose of verifying that it is possible to produce a high-quality single crystal with few pores with higher productivity even in a material system that is difficult to obtain.
  • sample for evaluation Film formation step Using a RF magnetron sputtering apparatus, on a titanium oxide (TiO 2 ) single crystal substrate (rutile, 10 mm ⁇ 10 mm square, 0.5 mm thickness, (100) plane), An amorphous layer of titanium oxide (TiO 2 ) having a thickness of 1.5 ⁇ m was formed. In the film formation, a commercially available titanium oxide (TiO 2 ) sintered body target was used. The film forming conditions were a pure Ar atmosphere, a pressure of 1 Pa, a room temperature, an input power of 120 W, and a film forming time of 120 minutes.
  • the amorphous film was heated using the heating apparatus shown in FIG. More specifically, the amorphous film was heated from the seed substrate side by irradiating near infrared rays from the side opposite to the surface on which the film of the seed substrate 202 was deposited.
  • the heating conditions were a heating temperature of 1000 ° C., a heating rate of 400 ° C./min, and a holding time of 10 minutes in a pure Ar atmosphere. Also in the sample according to this example, no change in film thickness was observed before and after the heating step.
  • zinc oxide (ZnO) doped with aluminum (Al) is formed on the surface of a seed substrate in which a single crystal of zinc oxide (ZnO) is formed on a sapphire (Al 2 O 3 ) substrate. This was carried out for the purpose of verifying that a single crystal having higher crystallinity can be obtained by producing a crystal layer as compared with the case where sapphire is used as a seed substrate.
  • the support substrate is heated to 700 ° C. using a resistance heater, and the zinc oxide having a thickness of 100 nm is controlled while controlling the flux of the gas source so that the stoichiometric ratio of zinc (Zn) and oxygen (O) is reached.
  • a single crystal layer of (ZnO) was formed as a seed substrate.
  • Zinc oxide (ZnO) doped with aluminum (Al) by the same procedure as in Experimental example 10 of Example 1 except that the seed substrate prepared in (1) above was used.
  • Single crystal Specifically, in the film forming step, zinc oxide (ZnO) powder in which aluminum (Al) is dissolved is formed on the surface of the seed substrate by the AD method, and in the heating step, FIG. Using the heating apparatus shown, the film was heated under the same conditions as in Experimental Example 10 of Example 1 described in Table 1. Note that a single crystal film of zinc oxide (ZnO) doped with aluminum (Al) having a thickness of 2.4 ⁇ m was formed by one cycle of the film forming step and the heating step. By repeating this cycle 100 times, a single crystal of zinc oxide (ZnO) doped with aluminum (Al) having a thickness of 240 ⁇ m could be produced.
  • Example 2 Evaluation Method of Sample for Evaluation
  • the following evaluation method was used as in Example 1.
  • (1) Cross-sectional SEM observation The cross section of the obtained single crystal was observed by SEM, and the presence or absence of pores in the cross section and the state of the interface between the single crystal and the seed substrate were evaluated.
  • (2) In-plane rocking curve (XRC) measurement The (100) peak detected by in-plane rocking curve (XRC) measurement was evaluated.
  • Evaluation Results of Various Evaluation Samples 40 fields of view from the end of the film in the cross section were observed with a scanning electron microscope (SEM) at a magnification of 5000, but no pores were observed. Further, the interface between the film and the seed substrate disappeared.
  • SEM scanning electron microscope
  • a sharper (100) peak was detected as compared with Experimental Example 10 of Example 1. That is, in this example, it was possible to produce a single crystal having higher crystallinity as compared with Experimental Example 10 of Example 1.
  • the heat treatment is performed in a state where warpage and / or undulation of the seed substrate is suppressed in the heating step, compared with the case where heat treatment is performed in a state where the warpage and / or undulation of the seed substrate is not suppressed, It carried out for the purpose of verifying that a single crystal having higher quality can be obtained.
  • Example 41 and 44 those obtained by correcting the warpage and / or undulation of the seed substrate are referred to as “Experimental Examples 41 and 44”, respectively, and the warpage and / or undulation of the seed substrate is corrected. Those not present are simply referred to as “Experimental Examples 01 and 04”, respectively.
  • Table 3 the seed substrates of Experimental Examples 41 and 44 in which the warpage and / or undulation of the seed substrate were corrected as described above showed warpage amounts of 2 ⁇ m and 5 ⁇ m, respectively. Furthermore, the quality (defect density) of the obtained single crystal was evaluated for each of the set of Experimental Example 01 and Experimental Example 41 and the set of Experimental Example 04 and Experimental Example 44.
  • the cross section by the plane orthogonal to the main surface of a seed substrate is observed by TEM, and the defect density of the single crystal obtained in each sample Asked. More specifically, it includes an interface between at least the seed substrate and a portion where the film formed is single-crystallized (hereinafter sometimes referred to as “single-crystallized portion”) from each evaluation sample that has undergone the heating step.
  • a section was cut out and processed by ion milling so that the thickness (T) of the section near the interface was 150 nm. The periphery of the interface of the section thus processed was observed with a TEM at a magnification of 50000 times, and a bright field image was taken.
  • a line segment having a length (L) of 5000 nm parallel to the interface between the single crystallized part and the seed substrate is separated from the interface by 400 nm, 800 nm, 1200 nm, 1600 nm, and 2000 nm.
  • a total of 5 lines were drawn at the locations, and the total number (S) of lattice defects present at positions overlapping these line segments was counted.
  • a value (D) [/ cm 2 ] calculated based on the following formula (2) is calculated as the defect density (D) [/ cm 2 ] of the single crystal from the total number S of lattice defects thus obtained. did.
  • the defect density (D) calculated for each sample for evaluation is also listed in Table 3.
  • the amount of warpage in the seed substrate corresponding to Experimental Example 01 of Example 1 subjected to heat treatment in the heating step included in the single crystal manufacturing method according to the present invention is suppressed from 50 ⁇ m to 2 ⁇ m.
  • the defect density in the resulting single crystal could be reduced from 5 ⁇ 10 8 pieces / cm 2 to 1 ⁇ 10 8 pieces / cm 2 .
  • the amount of warpage in the seed substrate corresponding to Experimental Example 04 of Example 1 subjected to the heat treatment in the heating step included in the single crystal manufacturing method according to the present invention is suppressed as a result from 90 ⁇ m to 5 ⁇ m.
  • the defect density in the obtained single crystal could be reduced from 7 ⁇ 10 8 pieces / cm 2 to 2 ⁇ 10 8 pieces / cm 2 .

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Abstract

L'invention concerne un monocristal qui est produit par formation d'abord, sur un substrat de germe, d'un film ayant une épaisseur de pas plus d'une valeur prescrite, et le chauffage de façon subséquente, à partir du côté de substrat de germe, du film résultant à une vitesse d'élévation de température d'au moins une valeur prescrite. De façon plus spécifique, dans une étape de formation de film dans laquelle le film est formé sur une surface du substrat de germe, le film est formé de façon à avoir une épaisseur de film, à savoir l'épaisseur dans une direction orthogonale à la surface du substrat de germe, de pas plus de 100 µm. De façon subséquente, dans une étape de chauffage dans laquelle le film formé sur la surface du substrat de germe est chauffé afin d'obtenir un monocristal, le film est chauffé à partir du côté du substrat de germe de telle sorte que la température est élevé à une vitesse d'élévation de température d'au moins 30°C/min. Comme résultat, l'invention concerne un procédé de production de monocristal qui présente une excellente productivité et qui est apte à produire des monocristaux de qualité élevée ayant peu de pores, non seulement lors de l'utilisation de matières avec lesquelles une matière de départ fondue est facilement obtenue, mais même lors de l'utilisation de matières avec lesquelles une matière de départ fondue est difficile à obtenir.
PCT/JP2013/082493 2012-12-14 2013-12-03 Procédé de production de monocristal, et monocristal produit à l'aide dudit procédé WO2014091968A1 (fr)

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JP2016130350A (ja) * 2015-01-14 2016-07-21 サムソン エレクトロ−メカニックス カンパニーリミテッド． コーティング膜を備える構造体およびその製造方法
KR20200102266A (ko) * 2019-02-21 2020-08-31 광운대학교 산학협력단 에어로졸 증착을 통한 니어 제로 TCR 및 고 접합 강도를 갖는 TiO2/Cu 복합 합성 필름의 제조 방법
CN113279058A (zh) * 2021-04-13 2021-08-20 中国科学院上海技术物理研究所 一种低对称性层状材料Te的可控制备方法
WO2022215621A1 (fr) * 2021-04-07 2022-10-13 信越化学工業株式会社 Procédé de fabrication de corps stratifié, dispositif de fabrication de corps stratifié, corps stratifié et dispositif semi-conducteur
CN115198356A (zh) * 2022-07-15 2022-10-18 郑州大学 一种特定取向的大规格金属单晶及其制备方法

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JP2016130350A (ja) * 2015-01-14 2016-07-21 サムソン エレクトロ−メカニックス カンパニーリミテッド． コーティング膜を備える構造体およびその製造方法
KR20200102266A (ko) * 2019-02-21 2020-08-31 광운대학교 산학협력단 에어로졸 증착을 통한 니어 제로 TCR 및 고 접합 강도를 갖는 TiO2/Cu 복합 합성 필름의 제조 방법
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CN113279058A (zh) * 2021-04-13 2021-08-20 中国科学院上海技术物理研究所 一种低对称性层状材料Te的可控制备方法
CN115198356A (zh) * 2022-07-15 2022-10-18 郑州大学 一种特定取向的大规格金属单晶及其制备方法

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