CN110817891B - Preparation method of nanoscale ultra-pure silicon oxide microsphere powder - Google Patents
Preparation method of nanoscale ultra-pure silicon oxide microsphere powder Download PDFInfo
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- CN110817891B CN110817891B CN201911272120.6A CN201911272120A CN110817891B CN 110817891 B CN110817891 B CN 110817891B CN 201911272120 A CN201911272120 A CN 201911272120A CN 110817891 B CN110817891 B CN 110817891B
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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
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a preparation method of nanoscale ultra-pure silicon oxide microsphere powder, which comprises the following steps: putting silicon into a first container, wherein the first container is made of graphite and is arranged in a closed reaction cavity with the ambient temperature of 50-150 ℃, the first container is connected with the anode of a current controller, and the cathode of the current controller is connected with an electron gun; the current controller is controlled to enable the electron gun to generate electron beams to bombard the silicon, so that the silicon generates silicon vapor molecules; after the silicon vapor molecules reach a certain pressure in the reaction cavity, introducing oxygen in a corresponding proportion into the reaction cavity, and controlling the working reaction pressure in the reaction cavity to be 2 multiplied by 10 ‑3 ～5×10 ‑3 Pa, reacting to obtain the silicon oxide microsphere powder. Silicon vapor molecules are generated after being bombarded by the electron beams and are combined with ultrahigh pure oxygen with a corresponding proportion introduced into the reaction cavity to react, and due to the combination among the molecules, the formed microspheres have small particle size, good roundness of the microspheres, low energy consumption and high production efficiency.
Description
Technical Field
The invention relates to the technical field of nano material powder preparation, in particular to a preparation method of nano-scale ultra-pure silicon oxide microsphere powder.
Background
In the field of electronic packaging, 97% of semiconductor devices all adopt Epoxy Molding Compound (EMC) as a packaging outer body material, a key insulating filling material in the epoxy molding compound is silicon oxide microsphere powder, the silicon oxide microsphere powder accounts for more than 70% of the components of the whole epoxy molding compound, a plurality of high-end chips are more than 90%, and the demand on the silicon oxide microsphere powder is increased year by year along with the annual and global increase of the demand on electronic products. In addition, in the field of electronic circuits, the insulating layer filler of electronic copper clad circuit board (CCL) is also used in silica microsphere powder, and the demand is increasing. Along with the increasing miniaturization of electronic products, the requirement on the integration level of electronic devices is higher, the corresponding requirement on the packaging size of the electronic devices is smaller and smaller, so that the performance requirements on all components in the plastic packaging material of the electronic devices are higher and higher, the granularity and the purity of the silicon oxide microsphere powder serving as a main filler in an epoxy plastic packaging material (EMC) directly influence the packaging molding size of the electronic devices and the electrical reliability of products, the granularity and the diameter of the silicon oxide microsphere powder used in the domestic packaging industry are generally more than 2 microns at present, and the silicon oxide microsphere powder with the nanometer diameter needs to be imported from Japan and other countries to purchase.
The traditional silicon oxide microsphere powder is prepared by mechanically crushing and processing a quartz ore, has the defects of large granularity diameter, uneven distribution, poor roundness of a sphere and the like, and in addition, natural quartz ore has the defects of difficult purification (the purity is below 99.999%) due to more impurities and overproof natural radiation, and directly influences the electrical reliability of a packaging device.
A method for preparing nano-scale silicon dioxide powder by adopting a solution method is also provided, for example, a patent with publication number CN 104709913A discloses a novel method for preparing nano-scale silicon dioxide powder, wherein a method of two-chamber electrolysis is adopted, the electrolysis current density of an inert electrode is controlled in an anode chamber, in a strong stirring environment, a method of reducing the pH value of sodium silicate solution in the anode chamber is adopted to obtain superfine silicic acid precipitate, and the superfine silicic acid precipitate is obtained by filtering, washing with deionized water, washing with absolute ethyl alcohol and drying, and the nano-scale silicon dioxide powder with the granularity controlled in the range of 60-85 nm can be obtained by pyrolysis at a certain temperature. The preparation operation technology of the method is more complex, the steps are more complicated, the roundness of the powder is poor, and the uniformity of the particles is poor.
Therefore, the traditional silicon oxide microsphere powder material is limited in the application field, and is difficult to develop better in the field of electronic technology packaging in the future era of Mole's law.
Disclosure of Invention
In order to solve the technical problems, the invention aims to: the preparation process of nanometer level superhigh purity silicon oxide microsphere powder includes electron beam bombardment of silicon material to produce silicon vapor molecule, introducing superhigh purity oxygen in certain proportion into the reaction cavity after the silicon vapor molecule reaches certain vapor pressure inside the reaction cavity, and combining the molecule with the molecule to form microsphere with small size (size of the particle size is normally Gaussian distribution, and the diameter of the silicon oxide microsphere may be controlled in 10-900 nm), high roundness, low power consumption, high operation performance and high production efficiency.
The technical scheme of the invention is as follows:
a preparation method of nanometer ultra-pure silicon oxide microsphere powder comprises the following steps:
s01: putting silicon into a first container, wherein the first container is made of graphite and is arranged in a closed reaction cavity with the ambient temperature of 50-150 ℃, the first container is connected with the anode of a current controller, and the cathode of the current controller is connected with an electron gun;
s02: the current controller is controlled to enable the electron gun to generate electron beams to bombard the silicon, so that the silicon generates silicon vapor molecules;
s03: after the silicon vapor molecules reach a certain pressure in the reaction cavity, introducing oxygen in a corresponding proportion into the reaction cavity, and controlling the working reaction pressure in the reaction cavity to be 2 multiplied by 10 -3 ～5×10 -3 Pa, reacting to obtain the silicon oxide microsphere powder.
In a preferred technical scheme, after the step S03, the method further includes detecting a pressure of the reaction chamber, and collecting the silicon oxide microsphere powder obtained by the reaction when a pressure change rate of the reaction chamber is smaller than a set threshold.
In a preferred technical scheme, the accelerating voltage provided to the anode by the current controller is 8-10 KV.
In a preferred technical scheme, the step S01 further comprises evacuating the reaction chamber before the reaction, wherein the pressure in the reaction chamber is 5 × 10 -6 ～5×10 -5 A negative pressure environment of Pa.
In a preferred technical solution, the introducing oxygen in a corresponding proportion in the step S03 includes controlling an inflow rate of oxygen to be the same as an evaporation rate of silicon molecules.
Compared with the prior art, the invention has the advantages that:
1. the method of the invention has subversive technology, is different from the traditional technical method, and fills the domestic blank in the field. The purity of the raw material can be manually controlled, the production cost is low, mechanical crushing processing and screening are not needed, the silicon oxide powder prepared by the method has few impurities and high purity, and the ultrahigh-purity silicon oxide powder with higher purity than natural quartz ore can be obtained by controlling the purity of the reaction source silicon raw material and the purity of oxygen.
2. The silicon vapor molecules can be generated after bombarding silicon by electron beams in a reaction cavity at a certain temperature, the ultrahigh pure oxygen with a corresponding proportion is introduced into the reaction cavity after the silicon vapor molecules reach a certain vapor pressure in the reaction cavity, and due to the combination between the molecules, the formed microspheres have small particle size (the particle size is in normal Gaussian distribution, and the diameter of the silicon oxide microspheres can be controlled to be 10-900 nanometers), the roundness of the microspheres is good, the silicon material is liquefied and vaporized into the microspheres at a high temperature to be oxidized to generate high sphericity, the energy consumption is low, and the production efficiency is high. The epoxy resin can be widely applied to the insulation filler of Epoxy Molding Compound (EMC) and the insulation filler of electronic copper clad circuit board (CCL) in the field of electronic packaging. In addition, the method can also be used in the technical fields of additives of paint, ink and coating, additives of daily cosmetics, preparation raw materials of high-purity optical fibers, processing raw materials of high-quality quartz pieces and the like.
Drawings
The invention is further described below with reference to the following figures and examples:
FIG. 1 is a flow chart of the preparation method of the nanometer ultra-pure silicon oxide microsphere powder of the invention;
FIG. 2 is a schematic structural diagram of an apparatus for preparing a nanoscale ultra-pure silica microsphere powder according to the present invention;
FIG. 3 is an SEM photograph of the silica microsphere powder prepared by the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
As shown in fig. 2, a device for preparing nanoscale microsphere powder comprises a reaction chamber 6, wherein the reaction chamber 6 is a closed chamber, the ambient temperature is 50-150 ℃, a first container 2 and an electron gun 3 are arranged in the reaction chamber 6, the first container 2 is made of graphite, for example, the first container 2 can be a crucible made of graphite, silicon 1 is arranged in the first container 2, the first container 2 is connected with an anode of a current controller 14, and a cathode of the current controller 14 is connected with the electron gun 3; the reaction chamber 6 is connected with a first pipeline 61 and a second pipeline 62, the first pipeline 61 is connected with the second oxygen through a flow controller 7, the second pipeline 62 is provided with a pressure regulating valve 17, and the second pipeline 62 is connected with a mechanical pump 12. The pressure regulating valve 17 is used for regulating the pressure inside the reaction chamber 6, and can also be used for discharging as a discharge valve.
A pressure sensor 18 is arranged in the reaction chamber 6 for detecting the pressure in the reaction chamber. The reaction chamber 6 is also connected with a third pipeline 63, and the third pipeline 63 is connected with a vacuum pump 15 through a vacuum pumping valve 16.
A heater 20 is arranged in the reaction chamber 6, and the heater 20 is connected with a temperature controller 19. The heater 20 is controlled by the temperature controller 19, and the temperature controller 19 monitors the change in the temperature inside the reaction chamber 6. The reaction chamber 6 and the second pipe 62 are made of stainless steel, and the inner walls thereof are mirror-polished, but may be made of other rigid materials to prevent the powder from being accumulated after the reaction.
The electron gun 3 is connected to a cooling circulation water system 21. For providing cooling of the electron gun 3 during operation.
The electron gun 3 is powered by a current controller 14 and emits an electron beam 4, the power of the electron gun 3 is 8-10 KW, the power can be adjusted by the current controller 14, the electron gun 3 is arranged at the cathode of the current controller 14, the crucible 2 is arranged at the anode of the current controller 14, the anode has an accelerating effect on the electron beam 4, the accelerating voltage provided by the current controller 4 to the anode is 8-10 KV, the electron beam 4 has directionality after being accelerated by the accelerating anode, and the electron beam 4 obtains kinetic energy after being accelerated to bombard silicon 1 in the crucible 2 of the anode.
The oxygen 10 is provided by an oxygen bottle 8, and the oxygen 10 is purified by a gas purifier 9, so that the purity reaches more than 99.9999 percent.
As shown in FIG. 1, a method for preparing nanoscale ultra-pure silicon oxide microsphere powder comprises the following steps:
(1) Putting the high-purity silicon material into a first container, wherein the first container is made of graphite material, for example, the first container can be a crucible made of graphite material, the silicon material 1 is monocrystalline silicon or polycrystalline silicon, preferably, the silicon material is in a fragmentary block shape or powder shape, the purity of the silicon material 1 is more than 99.9999%, and the high-purity silicon can be directly purchased;
(2) An electron gun 3 emits an electron beam 4 to bombard a silicon material 1 in a crucible 2, the electron gun 3 is provided with electric energy by a current controller 14 and emits an electron beam 4, the power of the electron gun 3 is 8-10 KW, the power can be adjusted by the current controller 14, the electron gun 3 is arranged at the cathode of the current controller 14, the crucible 2 is arranged at the anode of the current controller 14, the anode has an accelerating effect on the electron beam 4, the accelerating voltage provided by the current controller 4 to the anode is 8-10 KV, the electron beam 4 has directionality after being accelerated by the accelerating anode, the electron beam 4 obtains kinetic energy to bombard the silicon material 1 in the crucible 2 at the anode after being accelerated, and the silicon material 1 is bombarded by the electron beam 4 to generate silicon vapor molecules 5;
(3) In the figure 2, the reaction chamber 6 provides a closed reaction environment, the reaction chamber 6 needs to be vacuumized before reaction, the reaction chamber 6 needs to ensure that the discharge valve 17 is normally closed when the reaction chamber 6 is vacuumized, the reaction chamber 6 is vacuumized through the vacuum pump 15, and the vacuum degree needs to reach 5 multiplied by 10 -6 ～5×10 -5 Pa, when the reaction chamber 6 reaches the required vacuum degree, the vacuumizing valve 16 arranged at the vacuum pump 15 is closed, the electron gun 3 is opened to emit the electron beam 4, and silicon vapor molecules 5 generated after the silicon material 1 in the crucible 2 is bombarded by the electron beam 4 are rapidly diffused in the negative pressure environment of the reaction chamber 6 and fill the whole reaction chamber 6. When the reaction chamber 6 is reachedAfter a certain pressure is reached, the pressure is a preset pressure threshold value and can be set according to a specific environment, at this time, ultrahigh-purity oxygen 10 with a corresponding proportion is introduced into the reaction cavity 6, the introduced oxygen 10 is rapidly diffused and fully mixed in the reaction cavity 6 along with a negative pressure environment, silicon vapor molecules 5 and the oxygen 10 are rapidly diffused and fully mixed in a certain free path through the negative pressure environment of the reaction cavity 6, and the two are instantly oxidized and combined to form the nanoscale ultrahigh-purity silicon oxide microsphere powder 11 with the purity of more than 99.9999%.
The introduced oxygen 10 is provided by an oxygen bottle 8, the oxygen 10 is purified by a gas purifier 9, the purity of the oxygen 10 reaches more than 99.9999 percent, the introduction proportion of the oxygen 10 is controlled by a flow controller 7, the inflow of the oxygen 10 is determined by the evaporation amount of silicon vapor molecules 5, the oxygen and the silicon vapor molecules reach an equilibrium point to fully react, or the inflow rate of the oxygen is the same as the evaporation rate of the silicon molecules, the most intuitive reaction is the pressure of a pressure sensor 18, and the working reaction pressure in the reaction cavity 6 is controlled to be 2 multiplied by 10 -3 ～5×10 -3 Pa, the vacuum degree of the inner cavity of the reaction cavity 6 and the change condition of the reaction pressure are reflected by the pressure sensor 18. In the whole reaction process, the temperature of the reaction environment is kept between 50 and 150 ℃, the temperature of the reaction environment is reflected by the temperature controller 19 and fed back to the heater 20, the heater 20 is controlled to heat the internal environment of the cavity of the reaction cavity 6 so as to reach the required temperature, and the heating mode can be radio frequency heating or electric heating wire infrared heating;
(4) And (3) detecting the pressure of the reaction cavity in real time, when the pressure change rate of the reaction cavity is smaller than a set threshold value, namely the pressure of the reaction cavity tends to be stable, the threshold value is generally smaller than the pressure for reaction control, opening a discharge valve 17, pumping away the newly formed nano-scale ultra-pure silicon oxide microsphere powder 11 in the reaction cavity 6 through a pipeline 13 by a mechanical pump 12, collecting and bagging, and obtaining an SEM (scanning electron microscope) picture of the formed silicon oxide microsphere powder as shown in figure 3.
Reaction chamber 6 and pipeline 62 are all made by the stainless steel, and the complete mirror finish of inner wall 13 of reaction chamber 6 and all pipelines 62 has been handled for prevent that the powder from piling up at the inner wall of reaction chamber 6 and pipeline 62, prevent to arrange the material unsmooth because of piling up leading to, the length and the thickness of pipeline 62 are decided by the lift of mechanical pump 12, shorten the pipeline as far as in the lift scope of mechanical pump 12 and add thick pipeline, in order to guarantee to arrange the unobstructed of material.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundary of the appended claims, or the equivalents of such scope and boundary.
Claims (4)
1. A preparation method of nanometer ultra-pure silicon oxide microsphere powder is characterized by comprising the following steps:
s01: putting silicon into a first container, wherein the first container is made of graphite, the first container is placed in a closed reaction cavity with the ambient temperature of 50-150 ℃, the first container is connected with an anode of a current controller, and a cathode of the current controller is connected with an electron gun;
s02: the current controller is controlled to enable the electron gun to generate electron beams to bombard the silicon, so that the silicon generates silicon vapor molecules;
s03: after the silicon vapor molecules reach a certain pressure in the reaction cavity, introducing oxygen in a corresponding proportion into the reaction cavity, and controlling the working reaction pressure in the reaction cavity to be 2 multiplied by 10 -3 ～5×10 -3 Pa, reacting to obtain silicon oxide microsphere powder;
s04: and detecting the pressure of the reaction cavity, and when the pressure change rate of the reaction cavity is smaller than a set threshold value, pumping the newly formed nano-scale ultra-pure silicon oxide microsphere powder in the reaction cavity away by a mechanical pump through a pipeline, collecting and bagging.
2. The method for preparing nanoscale ultra-pure silicon oxide microsphere powder according to claim 1, wherein the accelerating voltage provided to the anode by the current controller is 8-10 KV.
3. The method for preparing the nanoscale ultra-high purity silicon oxide microsphere powder according to claim 1, wherein the step S01 further comprises evacuating the reaction chamber before the reaction, wherein the pressure in the reaction chamber is 5 x 10 -6 ～5×10 -5 A negative pressure environment of Pa.
4. The method for preparing nanoscale ultra-high purity silicon oxide microsphere powder according to claim 3, wherein the step S03 of introducing oxygen in a corresponding proportion comprises controlling the inflow rate of oxygen to be the same as the evaporation rate of silicon molecules.
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| CN102145893B (en) * | 2011-05-16 | 2012-11-07 | 青岛隆盛晶硅科技有限公司 | Method for purifying polysilicon by adopting electron beam to carry out fractionated smelting |
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