WO2005090234A1 - シリコン粒子、シリコン粒子超格子及びこれらの製造方法 - Google Patents
シリコン粒子、シリコン粒子超格子及びこれらの製造方法 Download PDFInfo
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- WO2005090234A1 WO2005090234A1 PCT/JP2005/002574 JP2005002574W WO2005090234A1 WO 2005090234 A1 WO2005090234 A1 WO 2005090234A1 JP 2005002574 W JP2005002574 W JP 2005002574W WO 2005090234 A1 WO2005090234 A1 WO 2005090234A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
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- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
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- 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
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- 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
- Y10T428/268—Monolayer with structurally defined element
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- Silicon particles Silicon particles, silicon particle superlattices, and methods for producing them
- the present invention relates to a high-purity silicon particle having a nanometer (nm) size and a method for producing the same.
- the present invention also relates to a silicon particle superlattice in which nanometer (nm) size silicon particles are regularly arranged two-dimensionally or three-dimensionally and a method for producing the same.
- Silicon particles having a particle size on the order of nanometers have attracted great interest in recent years as new functional materials because they have physical and chemical properties significantly different from those of bulk silicon.
- silicon nanoparticles have a band structure different from that of barta silicon based on quantum confinement effects and surface level effects, and a light emission phenomenon that is not observed in bulk silicon is observed. It is expected to be used as a raw material for devices!
- Ordinary silicon fine powder obtained by pulverizing silicon has physical and chemical properties almost identical to those of Balta silicon.
- silicon nanoparticles have a fine particle diameter and a relatively small particle size distribution width, and have high purity. For this reason, it is considered that unique properties such as a light emission phenomenon, which are remarkably different from those of normal silicon, are exhibited.
- methods for producing silicon nanoparticles include, for example, (1) silicon vaporized by a first high-temperature plasma generated between opposing silicon electrodes is placed in a decompressed atmosphere with V and electrodeless electrodes. Method of passing through the second high-temperature plasma generated by electric discharge (Patent Document 1), (2) Method of separating and removing anodic silicon nanoparticle formed of silicon wafer by electrochemical etching (Patent Document 2) (3) A method of reducing the halogen-containing organosilicon conjugate with an electrode using a reactive electrode (Patent Document 3) and the like have been used.
- the starting material is a halogen element such as C1. Since it is contained and easily mixed into the product, the total amount of Na, Fe, Al and CI is unlikely to be less than lOppm.
- nanometer-order silicon particles having a uniform particle size are periodically and regularly arranged two-dimensionally or three-dimensionally.
- An ordered, so-called superlattice structure must be formed.
- the above method (a) is often performed in a high-temperature vacuum or in a plasma atmosphere, so that a highly controlled vacuum heating device or plasma generation device is required, resulting in a high cost. .
- the method (b) does not require expensive equipment as the method (a), but the product yield is significantly reduced.
- particles are arranged on a porous partition or an electrode, but there is no appropriate method for desorbing a film or a molded product having a superlattice force from these materials.
- the conventional superlattice containing silicon particles obtained by these methods has instability in band structure and surface state due to variation in particle diameter, and when used as a light emitting element, emits light. Efficiency did not increase sufficiently, and there were concerns that malfunctions might occur when used as electronic components.
- Patent Document 1 JP-A-6-279015
- Patent Document 2 JP-T-2003-515459
- Patent Document 3 JP-A-2002-154817
- Patent Document 4 JP-A-5-62911
- Patent Document 5 JP-A-6-349744
- Patent Document 6 JP-A-11 130867
- Patent Document 7 JP-A-2002-279704
- Patent Document 8 JP-A-2003-89896
- the present inventors diligently studied whether there is a manufacturing method capable of producing high-purity silicon nanoparticles capable of realizing high-performance light-emitting elements and electronic components on an industrial scale. As a result, a method of removing excess silicon oxide with hydrofluoric acid after heat-treating silicon oxidized silicon particles encapsulated in silicon particles produced by a gas phase method using specific raw materials under specific conditions. As a result, they have found that high-purity nanometer-sized silicon particles having a relatively uniform particle size can be produced on an industrial scale, and have completed the present invention.
- the silicon particles of the present invention are characterized in that they have a particle size of 1 to 50 nm, and the total amount of Na, Fe, Al, and CI is 10 ppm or less.
- the silicon powder of the present invention is characterized by containing 90% by mass or more of silicon particles having a particle size of 1 to 50 nm and a total amount of Na, Fe, Al and CI of 10 ppm or less. .
- the silicon oxide particles encapsulating silicon particles are formed by reacting a monosilane gas and an oxidizing gas for oxidizing the monosilane gas in a gas phase.
- the present inventors have conducted intensive studies on a method for efficiently manufacturing a superlattice of silicon particles at a low cost, which can realize a high-performance light emitting element or electronic component, and as a result, completed the present invention. I came to.
- the silicon particle superlattice of the present invention is a silicon particle superlattice in which a plurality of silicon particle forces are also formed.
- the silicon particle has an average particle diameter of 150 nm and a coefficient of variation of particle diameter of 20 nm. % Or less.
- the method for producing a silicon particle superlattice of the present invention is characterized in that a suspension in which hydrophobic silicon particles are dispersed in water is added with a hydrophobic solvent, and then allowed to stand. Characterized in that it has a step of aligning silicon particles at the interface of, and that “the suspension contains hydrofluoric acid” and “the hydrophobic solvent is 11-year-old ketanol” are preferred. It is included.
- the silicon particle superlattice structure of the present invention is characterized in that the silicon particle superlattice is provided on a water-phobic surface of a solid substrate having a hydrophobic surface. Or a graphite substrate.
- the light emitting device and the electronic component of the present invention are characterized by having at least one of the silicon particle superlattice and the silicon particle superlattice structure.
- the silicon particles of the present invention are nanoparticles having a relatively uniform diameter of 1 to 50 nm, and have high purity with a total force of 10 ppm or less of Na, Fe, Al, and CI.
- silicon particles have a band structure different from that of barta silicon based on quantum confinement effects and surface state effects, and the particle size at which a light emission phenomenon is not observed in barta silicon is as follows.
- the quantum well structure which is important when applied to electronic components, is considered to be recognized as an aggregate of particles having a size equal to or less than lOnm.
- the silicon particles of the present invention have a particle size of 150 nm, which covers the range of the particle size at which the quantum confinement effect, surface level effect, or quantum well structure is exhibited.
- the silicon particles of the present invention have high utility as raw material powders for high-performance light-emitting devices and electronic components.
- the method for producing silicon particles of the present invention uses a specific silicon-containing gas Silane gas), reacting it with an oxidizing gas under specific conditions to synthesize silicon oxide containing silicon particles once, heat-treating it under specific conditions, and then adding excess hydrofluoric acid. It is a method of removing silicon oxide, and unlike the conventional method of producing silicon nanoparticles, it has high productivity and can be produced on an industrial scale. This makes it possible to apply silicon nanoparticles to light-emitting devices and electronic components on an industrial scale, which is very useful in industry.
- the silicon particles constituting the superlattice of the present invention are relatively uniform with an average particle diameter force of 50 nm, and the coefficient of variation of the particle diameter is 20% or less.
- a superlattice is a lattice-like particle aggregate in which particles consisting of atoms and molecules are further aggregated and regularly arranged two-dimensionally or three-dimensionally, but the variation in particle size is small. ! / The superlattice of the present invention is capable of stably producing a material having a desired band structure, since particles having a small surface level variation and excellent periodicity can be arranged.
- the silicon particle superlattice can create various band structures according to the purpose of use, sufficient luminous efficiency is obtained when used as a light emitting element, and when it is used as an electronic component. A material that is unlikely to malfunction can be created. Therefore, it is easy to improve the performance of electronic equipment, and it is very useful in industry, which greatly contributes to functional material manufacturing technology on an industrial scale.
- FIG. 1 is a TEM photograph showing an example of the silicon particle superlattice of the present invention.
- FIG. 2 is a Fourier transform image showing an example of the silicon particle superlattice of the present invention.
- the silicon particles of the present invention have a particle size of from 1 to 50 nm, preferably from 1 to 30 nm. If the particle size is out of this range, the quantum confinement effect, surface state effect, or quantum well structure suitable for application to light emitting devices and electronic components will not be exhibited.
- the total amount of Na, Fe, Al, and CI in the silicon particles of the present invention is 10 ppm or less, preferably 5 ppm or less. When the total amount of Na, Fe, Al, and CI exceeds 10 ppm, impurities may affect the characteristics of light emitting devices and electronic components. [0032] Ku silicon powder>
- the silicon powder of the present invention contains 90% by mass or more of the silicon particles of the present invention.
- the content of the silicon particles of the present invention is 90% by mass or more, unnecessary particles can be removed as it is or by a simple post-treatment.
- the content is less than 90% by mass, the removal of unnecessary particles becomes difficult.
- the silicon particles of the present invention are obtained, for example, by subjecting silicon oxide particles containing silicon particles synthesized from a gas phase to heat treatment at a predetermined atmosphere temperature using a monosilane gas and an oxidizing gas.
- a monosilane gas is reacted with an oxidizing gas in a gaseous phase.
- silicon oxide particles containing the silicon particles are synthesized.
- the reaction is carried out by introducing a monosilane gas and an oxidizing gas into a reaction vessel.
- the raw material serving as the silicon source in the present invention is monosilane gas.
- the total amount of Na, Fe, Al, and CI exceeds 10 ppm.
- the oxidizing gas is not particularly limited as long as it oxidizes the monosilane gas. Oxygen gas, air, water vapor, nitrogen dioxide, carbon dioxide and the like can be used. Oxygen gas is particularly preferred from the viewpoint of simplicity and ease of reaction control.
- inert gases such as argon and helium
- hydrogen, nitrogen, ammonia, and monoacid are used as long as they do not hinder the reaction.
- a third gas, such as carbon dioxide, can also be introduced into the reaction vessel.
- the reaction is preferably carried out while maintaining the temperature of the reaction vessel at 500 ° C to 1000 ° C and the pressure at 10 to 1000 kPa.
- the reaction vessel is generally made of a high-purity material such as quartz glass.
- the shape of the vessel is not particularly limited, but a tubular pipe is preferable in a vertical or horizontal direction. It may be.
- any method such as resistance heating, high-frequency induction heating, infrared radiation heating and the like can be used.
- the silicon oxide particles containing the silicon particles generated in the reaction vessel are discharged out of the system together with the gas flow, and collected from a powder collecting device such as a bag filter.
- the recovered silicon oxide particles are then kept at 800-1400 ° C under an inert atmosphere.
- the particle size of the silicon particles included in the silicon oxide sinter particles is adjusted to be 150 nm. If the holding temperature is lower than 800 ° C, the particle size of the silicon particles becomes smaller than lnm, impurities easily remain in the silicon, and the total amount of Na, Fe, Al, and CI exceeds lOppm. When the temperature exceeds 1400 ° C, the particle size of silicon particles exceeds 50 nm.
- inert atmosphere gas in addition to inert gases such as argon and helium, hydrogen, nitrogen, ammonia, carbon monoxide and the like can be used, but from the viewpoint of easy handling. Particularly, argon gas is preferable.
- the silicon oxide particles are added and dispersed in water. Dispersion is performed using an ultrasonic wave or a stirrer, and it is particularly preferable to use an ultrasonic wave.
- hydrofluoric acid is added to the suspension. The hydrofluoric acid does not dissolve the silicon particles contained in the silicon oxide particles, but dissolves and removes the surrounding silicon oxide particles, so that only the silicon remains and the silicon of the present invention is removed. Particles can be obtained.
- the average particle size of the silicon particles constituting the silicon particle superlattice of the present invention is 1 to 50 nm, preferably 5 to 20 nm. When the average particle size is less than 1 nm, it is difficult to arrange particles regularly. On the other hand, if the average particle size exceeds 50 nm, the physical properties of the balta silicon hardly change, and the meaning of forming a superlattice is lost.
- the coefficient of variation of the silicon particle diameter is 20% or less. If the variation coefficient of the particle size exceeds 20%, the variation of the particle size is too large to form a band.
- the “coefficient of variation in particle size” is a value obtained by dividing the standard deviation of the particle size by an average value, and is an index indicating the variation in the particle size. Means that the variance is small.
- a method of performing image analysis on a transmission electron microscope (TEM) image obtained by imaging a superlattice is exemplified.
- TEM transmission electron microscope
- whether or not a large number of particles are regularly arranged can be determined by a TEM image. More specifically, a force is determined by a Fourier transform image of a TEM image. it can. When the particles are regularly arranged, spots having symmetry corresponding to the formation of the lattice appear in the Fourier transform image. For example, FIG.
- FIG. 1 is a TEM image of an example of the silicon particle superlattice of the present invention
- FIG. 2 is a force that is a Fourier transform image thereof.In FIG. 2, six spots are observed in the Fourier transform image. It can be seen that a regularly arranged superlattice is formed.
- the method for producing a large number of silicon particles is not particularly limited as long as the obtained silicon particles have hydrophobicity.
- a monosilane gas and an oxidizing gas for oxidizing the monosilane gas are subjected to a gas phase reaction to synthesize silicon hydride particles containing silicon particles, which are then subjected to an inert atmosphere at 800 to 1400 ° C. Can be applied.
- the particle size of the silicon particles included in the silicon oxide is preferably adjusted to about 150 nm by heating and holding in an inert atmosphere.
- the silicon particle alignment step at the interface between the aqueous phase and the hydrophobic solvent the particle size is reduced, so that even if the variation at this point is relatively large, there is no problem. .
- the silicon oxide in the silicon oxide particles containing the silicon particles can be removed with hydrofluoric acid.
- this method is convenient because it simultaneously serves as a step of exposing silicon particles included in the silicon oxide object and imparting hydrophobicity to the surface of the silicon particles.
- hydrofluoric acid imparts hydrophobicity to the silicon particle surface is that the silicon oxide around the silicon particles is removed by hydrofluoric acid and hydrogen fluoride (HF It is thought that this is because the action of) causes a bond between the silicon atom and the hydrogen, and the particle surface is modified with the hydrogen atom.
- silicon oxide particles are dispersed in water in advance to form a suspension. If the acid is dropped, the silicon particles having hydrophobicity can be obtained in the form of a suspension, so that the method for producing a silicon particle superlattice of the present invention can be applied as it is, which is preferable. Further, in order to improve the dispersibility of the silicon particles, it is preferable to apply ultrasonic vibration to the suspension.
- a hydrophobic solvent is added to the suspension. This causes the silicon particles having hydrophobicity to move from the aqueous phase into the organic phase (hydrophobic solvent). At this time, in order to promote the movement of the particles, it is preferable to continuously apply ultrasonic vibration even after the addition of the hydrophobic solvent. When the silicon particles do not have hydrophobicity, no migration into the hydrophobic solvent occurs.
- the aqueous phase and the organic phase are separated, and the silicon particles dispersed in the hydrophobic solvent gradually gather and align at the interface between the aqueous phase and the organic phase.
- the particles having similar particle diameters are selectively aggregated and aligned, so that a superlattice having a silicon particle force is formed at the interface between the aqueous phase and the organic phase.
- a powder having a relatively large variation in particle size and a silicon particle force is used first, a large number of superlattices having different average particle sizes are formed at different locations on the interface.
- the solvent is not hydrophobic, no superlattice is formed because no interface between the aqueous phase and the organic phase occurs.
- hydrophobic solvent examples include water-insoluble or poorly water-soluble aliphatic hydrocarbon solvents such as n-hexane and n-hexane, and alicyclic rings such as cyclohexane and methylcyclohexane.
- hydrocarbon solvents aromatic hydrocarbon solvents such as toluene and xylene, and higher alcohols such as 1-butanol and 11-year-old ketanol.
- 1-octanol having a moderate viscosity is particularly preferred to facilitate the aggregation and alignment of silicon particles at the interface between the aqueous phase and the organic phase!
- the time for applying ultrasonic vibration after the addition of the hydrophobic solvent and the subsequent standing time are not particularly limited.
- the hydrophobic solvent is 1-octanol
- the ultrasonic vibration after addition is about 30 minutes to 1 hour.
- Subsequent standing is preferably for at least two days.
- the superlattice formed by the silicon particles formed at the interface between the aqueous phase and the organic phase as described above is, for example, scooped using a semipermeable membrane such as a collodion film and then solid substrate having a hydrophobic surface. By moving upward, a superlattice structure directly formed on the substrate can be obtained. Silicon substrates (silicon wafers) and dollars can be used as solid substrates with hydrophobic surfaces. And a fight substrate.
- the solid substrate having the hydrophobic surface is immediately placed at the interface between the aqueous phase and the organic phase so that the hydrophobic surface faces the hydrophobic solvent.
- a superlattice can be formed directly on a substrate having a hydrophobic surface.
- the hydrophobic region and the hydrophilic region are previously patterned on the substrate surface by lithography technology or the like, a superlattice can be formed at a desired position on the substrate.
- the superlattice structure of the present invention is formed directly on a silicon substrate, it can be used as a novel light emitting device or a device for a functional material such as an electronic component.
- Monosilane gas 0.16 LZmin, oxygen gas 0.4 LZmin and nitrogen gas for dilution 17.5 LZmin were placed in a reaction vessel consisting of a quartz glass reaction tube (inner diameter 50 mm, length 1000 mm) maintained at a temperature of 700 ° C and a pressure of 90 kPa. Upon introduction, a brown powder was produced. This was collected by a metal filter provided downstream of the reaction tube.
- the specific surface area of the collected powder was measured by the BET one-point method and found to be 55 m 2 / g.
- the main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and CI was 5 ppm. Furthermore, the particles of the powder contained in the powder were examined by transmission electron microscope (TEM). The diameter was measured to be 10-40 nm.
- the specific surface area of the collected product powder was measured and found to be 150 m 2 Zg.
- the main components were Si and oxygen, and the Si spectrum of XPS was examined.
- a silicon powder was obtained in the same manner as in Example 1 except that 20 g of this powder was kept at a temperature of 900 ° C for 1 hour in a helium atmosphere.
- the main component of this powder was Si, and the total amount of Na, Fe, Al, and CI was 8 ppm. Further, when the particle size was measured by TEM, it was 2 to 24 nm.
- a silicon powder was obtained in the same manner as in Example 1, except that 20 g of a powder containing silicon and having a silicon oxide sulfide particle strength was held at a temperature of 1450 ° C. for 1 hour in an argon atmosphere.
- the main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and CI was 4 ppm. Further, when the particle diameter of the particles was measured by TEM, it was found that the powder contained 12% by mass of the particles exceeding 50 nm and had a particle force of 35 nm or more.
- a silicon powder was obtained in the same manner as in Example 1, except that 20 g of a powder composed of silicon oxide particles containing Si was held at a temperature of 700 ° C for 1 hour in an argon atmosphere.
- the main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and CI was 18 ppm. Furthermore, the particle diameter of the particles was measured by TEM, and the powder contained 16% by mass of particles having a particle size of less than lnm and having a particle force of less than lOnm.
- the main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and CI was 23 ppm. Furthermore, the particle size of the particles was measured by TEM, and it was confirmed that the powder had a particle force of 6 nm or less, including 40% by mass of particles having a particle size of less than 1 nm.
- tetrachloride silicon Si is frequently used as a raw material for polycrystalline silicon.
- the specific surface area of the collected powder was measured and found to be 45 m 2 Zg.
- the main components were Si and oxygen, and the Si spectra of XPS were examined.
- a silicon powder was obtained in the same manner as in Example 1.
- the main component of this powder was Si, and the particle size of the particles measured by TEM was 5 to 35 nm.
- the powder contained a large amount of chlorine (C1) in particular, and the total amount of Na, Fe, Al, and CI was 50 ppm. .
- 0.116 LZmin of monosilane gas, 0.4 LZmin of oxygen gas, and 17.5 LZmin of nitrogen gas for dilution were placed in a reaction vessel consisting of a quartz glass reaction tube (inner diameter 50 mm, length 1000 mm) maintained at a temperature of 780 ° C and a pressure of 90 kPa. Upon introduction, a brown powder was produced. This was collected by a metal filter provided downstream of the reaction tube.
- the specific surface area of the collected powder was measured by the BET one-point method and found to be 62 m 2 / g.
- a brown powder was collected in the same manner as in Example 3 except that the temperature was changed to 700 ° C.
- the specific surface area of the powder was 42 m 2 Zg, and the main components by chemical analysis were silicon (Si) and oxygen (O).
- XPS showed a peak attributed to the Si—Si bond in addition to the peak attributed to the Si—O bond, confirming that the silicon particles were included in the generated silicon oxide hydride powder particles. .
- the silicon oxide hydride was dissolved and removed in the same manner as in Example 3 except that 2 g of this powder was kept at a temperature of 1100 ° C for 60 minutes in an argon atmosphere. Then, after adding 0.2 liter of xylene as a hydrophobic solvent, ultrasonic wave was applied for 30 minutes, and then left still for one day.
- a TEM sample was prepared in the same manner as in Example 3, except that the sample was dried for one day.
- a structural force in which the particles were regularly arranged was observed, and in the Fourier transform image, spots having six symmetry were observed, respectively, confirming the formation of a superlattice.
- 122 silicon particle images were sampled from the TEM image and image analysis was performed. As a result, the average particle diameter was l lnm, and the coefficient of variation of the particle diameter was 15%.
- Example 3 Thereafter, a TEM sample was prepared in the same manner as in Example 3.
- a structure in which the particles were regularly arranged was observed, and in the Fourier transform image, spots having six symmetry were observed, respectively, and the formation of a superlattice was confirmed.
- 147 silicon particle images were sampled from the TEM image and subjected to image analysis. As a result, the average particle diameter was 7 nm, and the coefficient of variation of the particle diameter was 17%.
- Silicon oxide particles containing silicon particles synthesized in the same manner as in Example 3, and 2 g of powder having power were held at a temperature of 1100 ° C. for 1 hour in an argon atmosphere, and then the same as in Example 3. Then, 0.2 l of 11-year-old ketanol was added as a hydrophobic solvent, and ultrasonic waves were applied for 30 minutes.
- the silicon wafer with the (111) surface exposed is horizontally inserted near the interface between the aqueous solution and the hydrophobic solvent so that the surface subjected to the hydrophobic treatment faces the hydrophobic solvent side (that is, the upper side).
- the silicon wafer was dried and the hydrophobized surface was observed with a field emission scanning electron microscope (FE-SEM). As a result, a structure in which particles were regularly arranged on the surface was observed. It was found that a superlattice of silicon particles was formed. As a result of sampling and image analysis of 105 silicon particle images obtained by the FE-SEM image, the average particle diameter was 5 nm, and the coefficient of variation of the particle diameter was 18%.
- FE-SEM field emission scanning electron microscope
- Silicon particles were directly deposited on the surface of the silicon wafer hydrophobized in the same manner as in Example 6 by a laser ablation method to form a film having a silicon particle force.
- a structure where particles were regularly arranged on the surface was partially observed, indicating that a superlattice of silicon particles had been formed.
- 167 silicon particle images obtained from the FE-SEM image were sampled and analyzed.As a result, the average particle diameter was 5 nm and the coefficient of variation of the particle diameter was 29%. there were.
- Example 3 after the 1-octanol had been cultivated, the mixture was not allowed to stand for 2 days, and immediately after the aqueous solution and the 11-year-old ketanol were separated, the silicon particles dispersed in the 11-year-old ketanol were immediately sucked up with a syringe. After dripping on the same support as in Example 3, it was dried at 60 ° C. for 3 days. When this was observed with a TEM, no arrangement structure of particles or spots in a Fourier transform image was observed, and it was found that a superlattice was formed.
- Example 5 In the same manner as in Example 5, a suspension of silicon particles was prepared. After adding 0.2 liter of xylene without adding hydrofluoric acid to the mixture, ultrasonic waves were applied for 30 minutes, and then allowed to stand for 1 day, but the silicon particles did not move into xylene and became hydrophobic. It was found that they did not have any.
- high-productivity, nanometer-sized silicon particle powder is synthesized on an industrial scale in large quantities without the need for a special electrolytic device or plasma generator.
- a new and high-performance luminescence can be achieved. It can contribute to the practical use of functional materials such as elements and electronic components.
- a superlattice made of nanometer-sized silicon particles can be manufactured with high productivity without requiring special expensive equipment and the like. Since the silicon particles constituting the silicon particles have a small variation in the particle diameter, the dispersion of the surface levels is small, and the particles can be arranged with excellent periodicity, so that a material having a desired band structure can be stably produced. . As described above, since the superlattice of the present invention can create various band structures according to the purpose of use, the material characteristics are stable even when used for functional materials such as novel light emitting devices and electronic components, Performance improvement is facilitated. Therefore, these functional materials can be contributed to practical use.
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CN2005800082566A CN1956920B (zh) | 2004-03-17 | 2005-02-18 | 硅粒子、硅粒子超晶格以及它们的制备方法 |
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JP2004076141A JP2005263536A (ja) | 2004-03-17 | 2004-03-17 | シリコン粒子超格子、その製造方法、及びそれを用いたシリコン粒子超格子構造物、並びに発光素子及び電子部品 |
JP2004-075521 | 2004-03-17 | ||
JP2004075521A JP4791697B2 (ja) | 2004-03-17 | 2004-03-17 | シリコン粒子の製造方法 |
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US12/823,314 Division US8221881B2 (en) | 2004-03-17 | 2010-06-25 | Silicon particle, silicon particle superlattice and method for producing the same |
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Cited By (2)
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CN100383037C (zh) * | 2006-06-08 | 2008-04-23 | 复旦大学 | 一种碳材料/纳米硅复合材料及其制备方法和应用 |
JP2016072286A (ja) * | 2014-09-26 | 2016-05-09 | 京セラ株式会社 | ナノ複合材料およびナノ複合材料分散溶液、ならびに光電変換装置 |
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EP2546321A4 (en) * | 2010-03-12 | 2014-05-14 | Bridgestone Corp | LIGHT-EMITTING BODY WITH SILICON MICROPARTICLES AND METHOD FOR PRODUCING A LIGHT-EMITTING BODY WITH SILICON MICROPARTICLES |
DE102011002599B4 (de) | 2011-01-12 | 2016-06-23 | Solarworld Innovations Gmbh | Verfahren zur Herstellung eines Silizium-Ingots und Silizium-Ingot |
JP5440661B2 (ja) | 2012-06-27 | 2014-03-12 | 株式会社豊田自動織機 | 珪素含有材料および珪素含有材料を含む二次電池用活物質 |
KR101583216B1 (ko) * | 2013-02-05 | 2016-01-07 | 주식회사 케이씨씨 | 실리콘 나노 입자의 연속 제조 방법 및 이를 포함하는 리튬이차전지용 음극활물질 |
JP2017104848A (ja) * | 2015-12-04 | 2017-06-15 | 小林 光 | シリコン微細ナノ粒子及び/又はその凝集体及び生体用水素発生材及びその製造方法並びに水素水とその製造方法及び製造装置 |
WO2020020458A1 (de) * | 2018-07-25 | 2020-01-30 | Wacker Chemie Ag | Thermische behandlung von siliziumpartikeln |
KR102574360B1 (ko) * | 2018-10-02 | 2023-09-01 | 와커 헤미 아게 | 리튬 이온 배터리의 애노드 활물질로서의, 특정 염소 함량을 갖는 규소 입자 |
CN112456498A (zh) * | 2020-11-12 | 2021-03-09 | 郑州中科新兴产业技术研究院 | 具有疏水包覆层的纳米硅材料、制备方法及应用 |
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JP2016072286A (ja) * | 2014-09-26 | 2016-05-09 | 京セラ株式会社 | ナノ複合材料およびナノ複合材料分散溶液、ならびに光電変換装置 |
Also Published As
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US20080131694A1 (en) | 2008-06-05 |
US7850938B2 (en) | 2010-12-14 |
US20100261007A1 (en) | 2010-10-14 |
US8221881B2 (en) | 2012-07-17 |
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