CN101570332B - Preparation method of high-purity low-radioactivity spherical silicon micropowder - Google Patents
Preparation method of high-purity low-radioactivity spherical silicon micropowder Download PDFInfo
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- CN101570332B CN101570332B CN2009100626372A CN200910062637A CN101570332B CN 101570332 B CN101570332 B CN 101570332B CN 2009100626372 A CN2009100626372 A CN 2009100626372A CN 200910062637 A CN200910062637 A CN 200910062637A CN 101570332 B CN101570332 B CN 101570332B
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Abstract
The invention discloses high-purity low-radioactivity spherical silicon micropowder. In the silicon micropowder, the content of SiO2 is not lower than 99.90 percent, the content of radioelement U is less than or equal to 1*10<-9>g/g, sphericization ratio is between 90 and 100 percent, and non-crystalline ratio is between 99 and 100 percent. The method for preparing the silicon micropowder comprises the following steps: preparing stable silica sol which has purity not lower than 99.90 percent and the ion content of an arbitrary impurity less than or equal to 5*10<-6>g/g by a silicon source with the content of radioelement U being less than or equal to 1*10<-9>g/g; concentrating the silica sol to lead the solid content of the silica sol to be between 41 and 70 percent; granulating the concentrated silica sol to lead grain diameter of the silica sol to be between 0.5 and 60 [mu]m; roasting the granulated silicon oxide micropowder at a temperature of between 500 and 1,100 DEG C; and carrying out sphericization treatment on the micropowder in a flame burner and a sphericizing furnace, and classifying and collecting the micropowder after cooling to obtain the high-purity low-radioactivity spherical silicon micropowder. The spherical silicon micropowder of the invention can meet the requirement of a large-scale integrated circuit on capsulation packing, and the invention has simple process, low cost, simple required equipment, and is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of high purity that is applied to large-scale integrated circuit encapsulation, low-radioactivity spherical silicon micropowder and preparation method thereof.
Background technology
Ball-shaped silicon micro powder is widely used in the encapsulation of semiconductor integrated circuit, and is more and more higher to the requirement of encapsulation filler along with development extensive, super large-scale integration, not only requires high-purity, ultra-fine, spheroidization, but also requires radioactive element content low.α-ray that radioelement in the packaged material sends makes to produce soft error by the unicircuit cisco unity malfunction, and destroys canned data in the unicircuit.When encapsulation 16M above storer, cause that by α-ray the problem that device produces soft error will become very outstanding.Thereby super large-scale integration has proposed strict more requirement to the radioactive element content of ball-shaped silicon micro powder.
At present, the method for preparing ball-shaped silicon micro powder mainly contains chemical method and physics method.Chinese patent CN1075154 reacts hydrolysis SiCl with invert emulsion
4, control the ratio of ratio, silicon and the water of certain stirring velocity and solvent and water, make ball-shaped silicon micro powder.Chinese patent CN188075 is a raw material with water glass and mineral acid, by the ratio of control solvent, emulsifying agent and water glass, and parameters such as rotating speed during emulsification and additive amount, preparation ball-shaped silicon micro powder.Ball-shaped silicon micro powder nodularization rate height, amorphous rate height, purity height, the radioactive element content of chemical process preparation are low.But the ball-shaped silicon micro powder of chemical process preparation is rough, loose density is low, flowability is poor, loading level is low.And chemical method synthesizing spherical silicon powder cost height pollutes environment easily.
Physical method mainly comprises direct-current plasma high-temperature melting method, radio-frequency plasma high-temperature melting method, carbon electrode high-temperature electric arc heating method, high-temperature fusion gunite etc., adopts the direct current-arc plasma method to prepare micron order and nano-grade spherical silica powder as Chinese patent CN1194807.Plasma sphereization method is owing to complex process equipment, and processing parameter is difficult to control, thereby is mainly used in experimental study.And, in prepared by physical method ball-shaped silicon micro powder technology, mostly be raw material (US Application 20030070452 with the natural quartz, JPA58145613, JPA11199219), because radioelement is difficult to remove in the natural quartz, can't make low-radioactivity spherical silicon micropowder.
In a word, although it is a lot of to prepare the method for ball-shaped silicon micro powder, but mostly have certain deficiency, or method cost height or easily environment is polluted or the ball-shaped silicon micro powder that can't prepare low-radioactivity spherical silicon micropowder or preparation can not satisfy the requirement of large-scale integrated circuit.Therefore, developing a kind of suitable large-scale integrated circuit uses low-radioactivity spherical silicon micropowder and preparation method thereof particularly important.
Summary of the invention
The purpose of this invention is to provide a kind of high purity, low-radioactivity spherical silicon micropowder and preparation method thereof.Adopt the ball-shaped silicon micro powder of this method preparation to have chemical method synthetic ball-shaped silicon micro powder purity height, characteristics that radioactive element content is low, have the ball-shaped silicon micro powder smooth surface of prepared by physical method, the characteristics that degree of mobilization is good, loose density is big, loading level is high again concurrently.And these method raw material sources are extensive, technology simple, be suitable for large-scale industrial production.
The technical scheme that realizes the object of the invention is: a kind of high purity, low-radioactivity spherical silicon micropowder, SiO in this silicon powder
2Content is not less than 99.90%, radioelement U content≤1 * 10
-9G/g, the spheroidization rate is 90～100%, the amorphous rate is 99～100%.
The granularity of above-mentioned silicon powder is 1～40 μ m.
The present invention also provides the preparation method of above-mentioned high purity, low-radioactivity spherical silicon micropowder, may further comprise the steps:
(1) with radioelement U content≤1 * 10
-9The silicon source of g/g is a raw material, and preparation purity is not less than 99.90% and wherein any impurity ion content is all≤5 * 10
-6The stabilized colloidal silica of g/g;
(2) silicon sol is concentrated, making its solid content is 41～70%;
(3) the silicon sol granulation after will concentrating, obtaining particle diameter is the class spherical silica micro mist of 0.5～60 μ m;
(4) ultrafine silica powder that granulation is obtained is in 500～1100 ℃ of thorough roastings;
(5) be the powder feeding carrier gas with nitrogen or oxygen, ultrafine silica powder after the roasting is axially introduced heating the flame that temperature is not less than 1750 ℃, quickened from flame burner, then the micro mist spheroidization stove that enters preheating further heat, fusion, after the cooling non-crystalline state silicon oxide that obtains is carried out classification, collection, obtain high purity, low-radioactivity spherical silicon micropowder.
Being powder feeding rate with the 15～300g/min ultrafine silica powder after with roasting in the above-mentioned steps (5) axially introduces heating the flame that temperature is not less than 1750 ℃, quickens from flame burner, then the micro mist spheroidization stove that enters preheating further heat, fusion.
Be as the powder feeding carrier gas with oxygen in the above-mentioned steps (5).
The flame flame flow velocity degree 10～30m/s of flame burner described in the above-mentioned steps (5).
Advantage of the present invention is as follows:
1. ball-shaped silicon micro powder purity height, the radioactive element content that adopts the inventive method to produce is low, spheroidization rate height, amorphous rate height, good fluidity, loading level height, particle diameter can be controlled, and is suitable for the large-scale integrated circuit encapsulation.
2. technical process of the present invention is simple, and cost is low, and required equipment is simple, is easy to accomplish scale production.
Description of drawings
Fig. 1 is the SEM figure of the embodiment of the invention 1 ball-shaped silicon micro powder.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
The preparation method of following examples is:
(1) with radioelement U content≤1 * 10
-9The silicon source of g/g is a raw material, preparation purity 〉=99.90% and wherein any impurity ion content is all≤5 * 10
-6The stabilized colloidal silica of g/g;
(2) silicon sol is concentrated, making its solid content (contained solid quality percentage composition in the silicon sol that promptly obtains at last) is 41～70%;
(3) the silicon sol granulation after will concentrating, obtaining particle diameter is the class spherical silica micro mist of 0.5～60 μ m;
(4) ultrafine silica powder that granulation is obtained is in 500～1100 ℃ of thorough roastings;
(5) be carrier gas with nitrogen or oxygen, ultrafine silica powder after the roasting is axially introduced heating the flame that temperature is not less than 1750 ℃, quickened from flame burner, micro mist enters that the spheroidization stove further heats, fusion then, after the cooling non-crystalline state silicon oxide that obtains is carried out classification, collection (ultrafine silica powder being carried out classification, collection as adopting the mode that gravity is collected, whirlwind is collected and cloth bag is collected), promptly obtain high purity, low-radioactivity spherical silicon micropowder.
Embodiment 1:
With radioelement U content≤1 * 10
-9The silicon source of g/g is the feedstock production silicon sol, and the purity of silicon sol is 99.98%, and (wherein any impurity ion content all≤5 * 10
-6G/g), it is 41% that silicon sol concentrates the back solid content, through air-flowing type mist projection granulating, grain graininess is 4.5 μ m, 800 ℃ of following roasting 1h, liquefied gas (LPG) is combustion gas, oxygen is combustion-supporting gas, oxygen is the powder feeding carrier gas, light a fire behind the pressure of adjusting oxygen, LPG and the flow, spheroidization stove preheating 50min (general preheating temperature is not less than 1500 ℃ and gets final product), powder feeding rate is 300g/min.Adopt SiO in the weighting method analysed preparation
2Content, ICP-MS detection of radioactive constituent content, laser particle analyzer are tested granularity and product are carried out SEM (the SEM figure of product as shown in Figure 1) and XRD analysis, SiO in the ball-shaped silicon micro powder that obtains
2Content is 99.96%, and radioelement U content is 0.05 * 10
-9G/g, middle footpath granularity is 3.2 μ m, and the spheroidization rate is 98%, and the amorphous rate is 100%.
Embodiment 2:
With radioelement U content≤1 * 10
-9The silicon source of g/g is the feedstock production silicon sol, and the purity of silicon sol is 99.98%, and (wherein any impurity ion content all≤5 * 10
-6G/g), it is 50% that silicon sol is concentrated the back solid content, grain graininess is 15.4 μ m after granulation, 800 ℃ of following roasting 1h, acetylene is combustion gas, oxygen is combustion-supporting gas, oxygen is the powder feeding carrier gas, light a fire behind the pressure of adjusting oxygen, acetylene and the flow, spheroidization stove preheating 50min, powder feeding rate is 100g/min.Analyze by the method identical, made SiO with embodiment 1
2Content is 99.96%, radioelement U content is 0.05 * 10
-9G/g, middle footpath granularity are that 9.6 μ m, spheroidization rate are 92%, the amorphous rate is 100% ball-shaped silicon micro powder.
Embodiment 3:
With radioelement U content≤1 * 10
-9The silicon source of g/g is the feedstock production silicon sol, and the purity of silicon sol is 99.99%, and (wherein any impurity ion content all≤5 * 10
-6G/g), it is 60% that silicon sol concentrates the back solid content, grain graininess is 40.6 μ m after granulation, 1100 ℃ of following roasting 40min, Sweet natural gas is combustion gas, oxygen is combustion-supporting gas, oxygen is the powder feeding carrier gas, light a fire behind the pressure of adjusting oxygen, Sweet natural gas and the flow, spheroidization stove preheating 50min, powder feeding rate is 50g/min.Analyze by the method identical, made SiO with embodiment 1
2Content is 99.96%, radioelement U content is 0.01 * 10
-9G/g, middle footpath granularity are that 22.6 μ m, spheroidization rate are 99%, the amorphous rate is 99% ball-shaped silicon micro powder.
Embodiment 4:
With radioelement U content≤1 * 10
-9The silicon source of g/g is the feedstock production silicon sol, and the purity of silicon sol is 99.99%, and (wherein any impurity ion content all≤5 * 10
-6G/g), it is 70% that silicon sol concentrates the back solid content, grain graininess is 59.8 μ m after granulation, 1000 ℃ of following roasting 60min, acetylene is combustion gas, oxygen is combustion-supporting gas, oxygen is the powder feeding carrier gas, light a fire behind the pressure of adjusting oxygen, acetylene and the flow, spheroidization stove preheating 50min, powder feeding rate is 15g/min.Methods analyst by identical with embodiment 1 makes SiO
2Content is 99.92%, radioelement U content is 0.01 * 10
-9G/g, middle footpath granularity are that 34.7 μ m, spheroidization rate are 92%, the amorphous rate is 100% ball-shaped silicon micro powder.
Silicon source among the above embodiment can be selected rice husk, elemental silicon for use, but is not limited to above-mentioned two kinds of silicon sources, as long as radioelement U content≤1 * 10 in the siliceous raw material
-9G/g gets final product; The processing method for preparing silicon sol by the silicon source can adopt ion exchange method or hydrolysis method but be not limited to above-mentioned preparation method, as long as the silicon sol of preparing is stable and SiO wherein
2Content is not less than 99.90% and wherein any impurity ion content is all≤5 * 10
-6G/g gets final product; The concentrating of silicon sol can be adopted the heating under vacuum concentration technology but to be not limited to above-mentioned concentration technology, if silicon sol is stable and its solid content between 41～70%; The prilling process of silicon sol can adopt centrifugal granulating or mist projection granulating but be not limited to above-mentioned granulation process, as long as the grain graininess that granulation obtains is between 0.5～60 μ m; The combustion gas of flame burner can be selected acetylene, Sweet natural gas or liquefied gas for use, but is not limited to above-mentioned combustion gas, as long as the flame temperature that burning produces is not less than 1750 ℃.
Claims (4)
1. the preparation method of a high purity, low-radioactivity spherical silicon micropowder is characterized in that may further comprise the steps:
(1) with radioelement U content≤1 * 10
-9The silicon source of g/g is a raw material, and preparation purity is not less than 99.90% and wherein any impurity ion content is all≤5 * 10
-6The stabilized colloidal silica of g/g;
(2) silicon sol is concentrated, making its solid content is 41～70%;
(3) the silicon sol granulation after will concentrating, obtaining particle diameter is the class spherical silica micro mist of 0.5～60 μ m;
(4) ultrafine silica powder that granulation is obtained is in 500～1100 ℃ of thorough roastings;
(5) be the powder feeding carrier gas with nitrogen or oxygen, ultrafine silica powder after the roasting is axially introduced heating the flame that temperature is not less than 1750 ℃, quickened from flame burner, micro mist enters that the spheroidization stove further heats, fusion then, after the cooling non-crystalline state silicon oxide that obtains is carried out classification, collection, obtain high purity, low-radioactivity spherical silicon micropowder, SiO in this silicon powder
2Content is not less than 99.90%, radioelement U content≤1 * 10
-9G/g, the spheroidization rate is 90～100%, the amorphous rate is 99～100%.
2. the preparation method of high purity according to claim 1, low-radioactivity spherical silicon micropowder, it is characterized in that: being powder feeding rate with the 15～300g/min ultrafine silica powder after with roasting in the step (5) axially introduces heating the flame that temperature is not less than 1750 ℃, quickens from flame burner, then the micro mist spheroidization stove that enters preheating further heat, fusion.
3. the preparation method of high purity according to claim 1, low-radioactivity spherical silicon micropowder is characterized in that: be as the powder feeding carrier gas with oxygen in the step (5).
4. the preparation method of high purity according to claim 1, low-radioactivity spherical silicon micropowder is characterized in that: the flame flame flow velocity degree 10～30m/s of flame burner described in the step (5).
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| CN103360793A (en) * | 2012-03-27 | 2013-10-23 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Low-dielectric constant filler and preparation technology thereof |
| CN102993816B (en) * | 2012-10-26 | 2015-01-21 | 雅安百图高新材料有限公司 | Titanium dioxide spherical composite oxide and preparation method thereof |
| US9969867B2 (en) * | 2013-05-20 | 2018-05-15 | Nissan Chemical Industries, Ltd. | Silica sol and silica-containing epoxy resin composition |
| CN106365172A (en) * | 2016-11-15 | 2017-02-01 | 中国海油石油总公司 | Preparation method of spherical silicon dioxide |
| WO2018186308A1 (en) * | 2017-04-05 | 2018-10-11 | 新日鉄住金マテリアルズ株式会社 | Spherical crystalline silica particles and method for producing same |
| CN107128935A (en) * | 2017-05-23 | 2017-09-05 | 苏州纳迪微电子有限公司 | A kind of preparation method of high-purity preparing spherical SiO 2 micro mist |
| CN109836849B (en) * | 2017-11-29 | 2021-02-05 | 浙江华飞电子基材有限公司 | Preparation method of spherical silicon dioxide with high balling rate |
| CN109455726A (en) * | 2018-12-14 | 2019-03-12 | 江苏联瑞新材料股份有限公司 | A kind of preparation method of ball-shaped silicon micro powder used for electronic packaging |
| CN109761205A (en) * | 2019-03-18 | 2019-05-17 | 青岛瓷兴新材料有限公司 | A kind of spherical beta silicon nitride powder of ultrapure low-activity, its manufacturing method and application |
| CN112591756A (en) * | 2020-11-30 | 2021-04-02 | 江苏联瑞新材料股份有限公司 | High-purity low-radioactivity spherical silicon micro powder and preparation method thereof |
| CN112573529B (en) * | 2020-12-15 | 2023-08-15 | 江苏中腾石英材料科技股份有限公司 | Preparation process and equipment of high-purity low-radiation spherical silicon micro powder for 5G base station |
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| CN1075154A (en) * | 1993-03-03 | 1993-08-11 | 复旦大学 | A kind of preparation method who is used for the filler-silicon dioxide of epoxy mold sealing material |
| CN1381304A (en) * | 2002-01-08 | 2002-11-27 | 纪崇甲 | DC arc plasma equipment and process for preparing micron-class and nano-class powder material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075154A (en) * | 1993-03-03 | 1993-08-11 | 复旦大学 | A kind of preparation method who is used for the filler-silicon dioxide of epoxy mold sealing material |
| CN1381304A (en) * | 2002-01-08 | 2002-11-27 | 纪崇甲 | DC arc plasma equipment and process for preparing micron-class and nano-class powder material |
Non-Patent Citations (2)
| Title |
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| JP昭58-145613A 1983.08.30 |
| 张军等.高纯超细电子级球形石英粉研究.《电子元件与材料》.2004,第23卷(第1期),48-51. * |
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