JP2005263522A - Silicon particles, silicon powder and method for manufacturing silicon particles - Google Patents
Silicon particles, silicon powder and method for manufacturing silicon particles Download PDFInfo
- Publication number
- JP2005263522A JP2005263522A JP2004075521A JP2004075521A JP2005263522A JP 2005263522 A JP2005263522 A JP 2005263522A JP 2004075521 A JP2004075521 A JP 2004075521A JP 2004075521 A JP2004075521 A JP 2004075521A JP 2005263522 A JP2005263522 A JP 2005263522A
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- particles
- powder
- gas
- silicon particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
本発明は、ナノメートル（ｎｍ）サイズの高純度シリコン粒子及びその製造方法に関する。 The present invention relates to nanometer (nm) size high-purity silicon particles and a method for producing the same.
ナノメートルオーダーの粒径を有するシリコン粒子（以下、「シリコンナノ粒子」と言う。）は、バルクシリコンとは著しく異なる物理的、化学的性質を有するため、近年、新規機能性材料として大きな関心を集めている。例えば、シリコンナノ粒子は、量子論的閉じ込め効果や表面準位効果に基づく、バルクシリコンとは異なるバンド構造を有しており、バルクシリコンでは観測されない発光現象が認められるため、新規なシリコン発光デバイス用原料としての応用が期待されている。 Silicon particles having a particle size on the order of nanometers (hereinafter referred to as “silicon nanoparticles”) have physical and chemical properties that are significantly different from those of bulk silicon. Collecting. For example, silicon nanoparticles have a band structure different from bulk silicon based on quantum confinement effects and surface level effects, and light emission phenomena that are not observed in bulk silicon are observed. Application as a raw material is expected.
シリコンを微粉砕して得られる通常のシリコン微粉末は、バルクシリコンとほぼ一致する物理的、化学的性質を有している。これに対し、シリコンナノ粒子は、粒径が微細で粒度分布幅が比較的小さく、しかも高純度である。このため、バルクシリコンとは著しく異なる、発光現象等の特異な性質が発現すると考えられている。 Ordinary silicon fine powder obtained by finely pulverizing silicon has physical and chemical properties almost identical to bulk silicon. In contrast, silicon nanoparticles have a fine particle size, a relatively small particle size distribution width, and high purity. For this reason, it is thought that peculiar properties, such as a luminescence phenomenon, which are remarkably different from bulk silicon are expressed.
従来、シリコンナノ粒子の製造方法としては、例えば、（１）対向するシリコン電極間で発生させた第一の高温プラズマによって蒸発させたシリコンを、減圧雰囲気中において無電極放電で発生させた第二の高温プラズマ中に通過させる方法（特許文献１）、（２）電気化学的エッチングによって、シリコンウェハーからなる陽極からシリコンナノ粒子を分離・除去する方法（特許文献２）、（３）含ハロゲン有機シリコン化合物を、反応性電極を用いて電極還元する方法（特許文献３）等が用いられてきた。 Conventionally, as a method for producing silicon nanoparticles, for example, (1) a second method in which silicon evaporated by a first high-temperature plasma generated between opposing silicon electrodes is generated by electrodeless discharge in a reduced-pressure atmosphere. (2) Method of separating and removing silicon nanoparticles from an anode made of a silicon wafer by electrochemical etching (Patent Document 2), (3) Halogen-containing organic A method of electrode reduction of a silicon compound using a reactive electrode (Patent Document 3) has been used.
しかし、上記（１）、（２）の方法は、シリコンナノ粒子の生成速度が著しく小さいため、生産性向上が困難である。また、上記（３）の方法は、原料がＣｌ等のハロゲン元素を含んでおり、これが生成物に混入しやすいため、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量１０ｐｐｍ以下にはなり難い。 However, in the methods (1) and (2), it is difficult to improve productivity because the production rate of silicon nanoparticles is extremely low. In the method (3), since the raw material contains a halogen element such as Cl, which is likely to be mixed into the product, the total amount of Na, Fe, Al, and Cl is less than 10 ppm.
従って、高性能な発光素子や電子部品用の原料粉末として有用な、高純度のシリコンナノ粒子を工業的な規模で生産することは、極めて困難であった。 Therefore, it has been extremely difficult to produce high-purity silicon nanoparticles useful as a raw material powder for high-performance light-emitting elements and electronic parts on an industrial scale.
そこで、本発明者等は高性能な発光素子や電子部品が実現可能な、高純度のシリコンナノ粒子を、工業的規模で生産可能な製造方法がないか鋭意検討した。その結果、特定の原料を用いて気相法で作製した、シリコン粒子内包シリコン酸化物を、特定の条件で加熱処理した後にフッ化水素酸で余分のシリコン酸化物を除去する方法によって、粒径が比較的揃った高純度のナノメートルサイズのシリコン粒子が、工業的規模で製造可能であることを見出し、本発明を完成するに至った。 Therefore, 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, the silicon particle-containing silicon oxide produced by a vapor phase method using a specific raw material was heated under specific conditions, and then the excess silicon oxide was removed with hydrofluoric acid. As a result, it was found that high-purity nanometer-sized silicon particles having a relatively uniform diameter can be produced on an industrial scale, and the present invention has been completed.
すなわち、本発明のシリコン粒子は、粒径が１〜５０ｎｍであり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量が１０ｐｐｍ以下であることを特徴とする。 That is, the silicon particles of the present invention have a particle size of 1 to 50 nm and a total amount of Na, Fe, Al, and Cl is 10 ppm or less.
また、本発明のシリコン粉末は、粒径が１〜５０ｎｍであり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量が１０ｐｐｍ以下であるシリコン粒子を９０質量％以上含有することを特徴とする。 In addition, the silicon powder of the present invention is characterized by containing 90% by mass or more of silicon particles having a particle diameter of 1 to 50 nm and a total amount of Na, Fe, Al, and Cl of 10 ppm or less.
さらに、本発明のシリコン粒子の製造方法は、モノシランガスと、該モノシランガスを酸化するための酸化性ガスとを気相反応させて、シリコン粒子を内包するシリコン酸化物粒子を含む粉末を合成する工程と、該粉末を不活性雰囲気下８００〜１４００℃で保持した後、フッ化水素酸にて前記シリコン酸化物を除去する工程を有することを特徴とする。 Furthermore, the method for producing silicon particles of the present invention includes a step of synthesizing a powder containing silicon oxide particles containing silicon particles by causing a gas phase reaction between monosilane gas and an oxidizing gas for oxidizing the monosilane gas. The method further comprises a step of removing the silicon oxide with hydrofluoric acid after holding the powder at 800 to 1400 ° C. under an inert atmosphere.
本発明のシリコン粒子は、粒径が１〜５０ｎｍで比較的揃ったナノ粒子であり、しかもＮａ，Ｆｅ，Ａｌ，Ｃｌの合計量が１０ｐｐｍ以下であり高純度である。 The silicon particles of the present invention are nanoparticles having a relatively uniform particle size of 1 to 50 nm, and the total amount of Na, Fe, Al, and Cl is 10 ppm or less and has high purity.
一般に、シリコン粒子が、量子論的閉じ込め効果や表面準位効果に基づくバルクシリコンとは異なるバンド構造を有し、バルクシリコンでは観測されない発光現象を示す際の粒径は、１〜５ｎｍとされており、電子部品に適用する際に重要になる量子井戸構造は、１０ｎｍ以下でかつ揃った粒径を有する粒子の集合体において認められるとされている。本発明のシリコン粒子の粒径は１〜５０ｎｍであり、これらの量子論的閉じ込め効果、表面準位効果あるいは量子井戸構造が発現する粒径の範囲を包含している。 In general, silicon particles have a band structure different from that of bulk silicon based on the quantum confinement effect and the surface level effect, and the particle size when exhibiting a light emission phenomenon that is not observed in bulk silicon is 1 to 5 nm. In addition, it is said that the quantum well structure that is important when applied to an electronic component is recognized in an aggregate of particles having a uniform particle size of 10 nm or less. The particle size of the silicon particles of the present invention is 1 to 50 nm, and includes the range of particle sizes in which the quantum confinement effect, surface level effect, or quantum well structure is manifested.
また、シリコンがＮａ，Ｆｅ，ＡｌあるいはＣｌなどの不純物を含むと、バンド構造内に不純物準位が形成されてこれが発光素子における発光効率の低下や電子部品の誤動作を引き起してしまう。本発明のシリコン粒子のＮａ，Ｆｅ，Ａｌ，Ｃｌの合計量は１０ｐｐｍ以下であるため、不純物準位は形成されず、発光素子や電子部品における上記の不具合は生じない。 In addition, when silicon contains impurities such as Na, Fe, Al, or Cl, impurity levels are formed in the band structure, which causes a decrease in light emission efficiency in the light emitting element and malfunction of electronic components. Since the total amount of Na, Fe, Al, and Cl of the silicon particles of the present invention is 10 ppm or less, no impurity level is formed, and the above-described problems in the light emitting element and the electronic component do not occur.
このため本発明のシリコン粒子は、従来のシリコンナノ粒子とは異なり高性能な発光素子や電子部品用の原料粉末としての実用性が高い。 Therefore, unlike the conventional silicon nanoparticles, the silicon particles of the present invention are highly practical as a raw material powder for high-performance light-emitting elements and electronic parts.
また、本発明のシリコン粒子の製造方法は、原料として特定のシリコン含有気体（モノシランガス）を用い、これを特定の条件で酸化性ガスと反応させて一旦シリコン粒子を内包するシリコン酸化物を合成し、さらにこれを特定の条件で加熱処理した後にフッ化水素酸で余分のシリコン酸化物を除去する方法であり、従来のシリコンナノ粒子製造方法とは異なり、生産性が高く工業的規模での生産も可能である。このため、工業的規模でのシリコンナノ粒子の発光素子や電子部品への適用が可能になり、産業上非常に有用である。 In addition, the silicon particle production method of the present invention uses a specific silicon-containing gas (monosilane gas) as a raw material, reacts with an oxidizing gas under specific conditions, and synthesizes a silicon oxide once containing silicon particles. In addition, this is a method in which excess silicon oxide is removed with hydrofluoric acid after heat treatment under specific conditions. Unlike conventional silicon nanoparticle production methods, it is highly productive and produced on an industrial scale. Is also possible. For this reason, it becomes possible to apply silicon nanoparticles to light-emitting elements and electronic components on an industrial scale, which is very useful industrially.
本発明のシリコン粒子は、粒径が１〜５０ｎｍ、好ましくは１〜３０ｎｍである。粒径がこの範囲を外れると、発光素子や電子部品への応用に適した量子論的閉じ込め効果、表面準位効果、あるいは量子井戸構造が発現しない。また、本発明のシリコン粒子のＮａ，Ｆｅ，Ａｌ，Ｃｌの合計量は１０ｐｐｍ以下、好ましくは５ｐｐｍ以下である。Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量が１０ｐｐｍを超えると、発光素子や電子部品の特性に不純物の影響が生じ得る。 The silicon particles of the present invention have a particle size of 1 to 50 nm, preferably 1 to 30 nm. If the particle size is out of this range, the quantum confinement effect, surface level effect, or quantum well structure suitable for application to light-emitting elements and electronic components will not be exhibited. Further, the total amount of Na, Fe, Al and Cl 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 Cl exceeds 10 ppm, the influence of impurities may occur on the characteristics of the light emitting element and the electronic component.
本発明のシリコン粉末は、本発明のシリコン粒子を９０質量％以上含有する。本発明シリコン粒子の含有量が９０質量％以上であれば、そのまま、または簡便な後処理で不要粒子を除去することができるが、９０質量％未満では不要粒子の除去が容易でなくなる。 The silicon powder of the present invention contains 90% by mass or more of the silicon particles of the present invention. If 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 simple post-treatment, but if it is less than 90% by mass, removal of unnecessary particles is not easy.
本発明のシリコン粒子は、例えば、モノシランガスと酸化性ガスを用いて気相から合成したシリコン粒子含有シリコン酸化物粒子を所定の雰囲気・温度で加熱処理した後、シリコン酸化物を除去することにより製造することができる。 The silicon particles of the present invention are produced, for example, by removing silicon oxide after heat-treating silicon particle-containing silicon oxide particles synthesized from a gas phase using monosilane gas and oxidizing gas at a predetermined atmosphere and temperature. can do.
具体的には、ます、モノシランガスを酸化性ガスと気相中で反応させることによって、シリコン粒子を内包するシリコン酸化物粒子を含む粉末が合成される。反応は、反応容器内にモノシランガスと酸化性ガスを導入することによって行われる。 Specifically, by reacting monosilane gas with oxidizing gas in the gas phase, a powder containing silicon oxide particles containing silicon particles is synthesized. The reaction is performed by introducing monosilane gas and oxidizing gas into the reaction vessel.
ここで、本発明においてシリコン源となる原料は、モノシランガスである。モノシランガス以外のシリコン含有気体、例えばクロロシラン類（ＳｉＨnＣｌ4-n、ｎ＝０〜３の整数）を原料として用いると、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量が１０ｐｐｍを超える。 Here, the raw material which becomes a silicon source in the present invention is monosilane gas. When a silicon-containing gas other than monosilane gas, for example, chlorosilanes (SiH n Cl 4-n , n = 0 to 3) is used as a raw material, the total amount of Na, Fe, Al, and Cl exceeds 10 ppm.
酸化性ガスは、モノシランガスを酸化させるものであれば特に限定されないが、酸素ガス、空気、水蒸気、二酸化窒素、二酸化炭素等を用いることができ、取扱いの簡便性、反応制御の容易性等の点から、特に酸素ガスが好ましい。また、反応制御を容易にするために、モノシランガス及び酸化性ガスを希釈する目的で、アルゴン、ヘリウムのような不活性ガスの他、反応を妨げない限りで、水素、窒素、アンモニア、一酸化炭素等の第三のガスを反応容器内に導入することもできる。 The oxidizing gas is not particularly limited as long as it oxidizes monosilane gas, but oxygen gas, air, water vapor, nitrogen dioxide, carbon dioxide, etc. can be used, and the points such as easy handling and ease of reaction control can be used. Therefore, oxygen gas is particularly preferable. In order to facilitate the reaction control, hydrogen, nitrogen, ammonia, carbon monoxide, as well as inert gases such as argon and helium, as well as inert gases such as argon and helium, are used for the purpose of diluting monosilane gas and oxidizing gas. A third gas such as can also be introduced into the reaction vessel.
反応は、反応容器の温度を５００℃〜１０００℃、圧力を１０〜１０００ｋＰａに保持して行うことが好ましい。反応容器は、石英ガラス等の高純度材料で作製されたものが一般的に使用され、その形状は特に制限が無いが管状が好ましく、管の軸方向は、垂直、水平何れの方向であっても良い。反応容器の加熱方式については、抵抗加熱、高周波誘導加熱、赤外線輻射加熱等、任意の方式を用いることができる。 The reaction is preferably carried out while maintaining the temperature of the reaction vessel at 500 to 1000 ° C. and the pressure at 10 to 1000 kPa. A reaction vessel made of a high-purity material such as quartz glass is generally used, and its shape is not particularly limited, but a tube is preferred, and the axial direction of the tube is either vertical or horizontal. Also good. As for the heating method of the reaction vessel, any method such as resistance heating, high frequency induction heating, infrared radiation heating and the like can be used.
反応容器内で生成したシリコン粒子を内包するシリコン酸化物粒子を含む粉末は、ガス流とともに系外へ排出され、バグフィルター等の粉末捕集装置から回収される。 The powder containing silicon oxide particles containing silicon particles generated in the reaction vessel is discharged out of the system together with the gas flow, and is collected from a powder collecting device such as a bag filter.
回収された粉末は、次いで不活性雰囲気下８００〜１４００℃で保持される。かかる処理によって、粉末のシリコン酸化物粒子に内包されるシリコン粒子の粒径が１〜５０ｎｍに調整される。保持温度が８００℃未満では、シリコン粒子の粒径が１ｎｍ未満になるし、不純物がシリコン中に残留しやすくなり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量が１０ｐｐｍを超えてしまう。また１４００℃を超えると、シリコン粒子の粒径が５０ｎｍを超える。 The recovered powder is then held at 800-1400 ° C. under an inert atmosphere. By such treatment, the particle size of the silicon particles included in the powdered silicon oxide particles is adjusted to 1 to 50 nm. When the holding temperature is less than 800 ° C., the particle size of the silicon particles is less than 1 nm, impurities are likely to remain in the silicon, and the total amount of Na, Fe, Al, and Cl exceeds 10 ppm. Moreover, when it exceeds 1400 degreeC, the particle size of a silicon particle will exceed 50 nm.
不活性雰囲気ガスとしては、アルゴン、ヘリウムのような不活性ガスの他、水素、窒素、アンモニア、一酸化炭素等も使用可能ではあるが、取扱いの簡便性等の点から、特にアルゴンガスが好ましい。 As the inert atmosphere gas, hydrogen, nitrogen, ammonia, carbon monoxide and the like can be used in addition to an inert gas such as argon and helium, but argon gas is particularly preferable from the viewpoint of easy handling and the like. .
内包するシリコン粒子の粒径調整後、シリコン酸化物粒子を含む粉末は、水中に添加・分散される。分散は、超音波や攪拌機を用いて行われるが、特に超音波を用いることが好ましい。粉末が水中に分散して懸濁化した後、この懸濁液にフッ化水素酸が添加される。フッ化水素酸によって、シリコン酸化物粒子に内包されるシリコン粒子は溶解しないが、周囲のシリコン酸化物は溶解・除去されるため、シリコンのみが残存して本発明のシリコン粒子を得ることができる。 After adjusting the particle size of the silicon particles to be included, the powder containing the silicon oxide particles is added and dispersed in water. The dispersion is performed using ultrasonic waves or a stirrer, and it is particularly preferable to use ultrasonic waves. After the powder is dispersed and suspended in water, hydrofluoric acid is added to the suspension. The silicon particles contained in the silicon oxide particles are not dissolved by hydrofluoric acid, but the surrounding silicon oxide is dissolved and removed, so that only the silicon remains and the silicon particles of the present invention can be obtained. .
以下、実施例及び比較例をあげて、さらに本発明を説明する。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.
＜実施例１＞
モノシランガス０．１６Ｌ／ｍｉｎ、酸素ガス０．４Ｌ／ｍｉｎ及び希釈用の窒素ガス１７．５Ｌ／ｍｉｎを、温度７００℃、圧力９０ｋＰａに保持した石英ガラス製反応管（内径５０ｍｍ、長さ１０００ｍｍ）からなる反応容器に導入したところ、茶褐色の粉末が生成した。これを反応管の下流側に設けた金属製フィルターで捕集した。
<Example 1>
From a quartz glass reaction tube (inner diameter 50 mm, length 1000 mm) in which monosilane gas 0.16 L / min, oxygen gas 0.4 L / min and dilution nitrogen gas 17.5 L / min were maintained at a temperature of 700 ° C. and a pressure of 90 kPa. When introduced into a reaction vessel, a brown powder was produced. This was collected with a metal filter provided on the downstream side of the reaction tube.
捕集した生成粉末の比表面積をＢＥＴ１点法で測定したところ５５ｍ2／ｇであった。化学分析を行ったところ、主成分はシリコン（Ｓｉ）及び酸素（Ｏ）であった。またＸＰＳ（Ｘ線光電子スペクトル）のＳｉ2pスペクトルによってＳｉの結合状態を調べた結果、Ｓｉ−Ｏ結合に帰属されるピークの他に、Ｓｉ−Ｓｉ結合に帰属されるピークが認められ、生成したシリコン酸化物粒子にシリコン粒子が内包されていることが確認された。 It was 55 m < 2 > / g when the specific surface area of the collected produced | generated powder was measured by the BET 1 point method. When chemical analysis was performed, the main components were silicon (Si) and oxygen (O). Moreover, as a result of examining the bonding state of Si by the XPS (X-ray photoelectron spectrum) Si 2p spectrum, in addition to the peak attributed to the Si—O bond, a peak attributed to the Si—Si bond was observed and produced It was confirmed that silicon particles were included in the silicon oxide particles.
この粉末２０ｇをアルゴン雰囲気下、１１００℃の温度で１時間保持した後、室温まで冷却し、蒸留水１リットルを加え、さらに超音波を１時間かけて粉末を分散させ、懸濁液を作製した。これに濃度５％のフッ化水素酸（ＨＦ）０．１リットルを加えて超音波を３０分間かけ、シリコン酸化物を溶解・除去した。その後メンブレンフィルターを用いて懸濁液を濾過・洗浄して生成物を分離し、乾燥してシリコン粉末を得た。 After maintaining 20 g of this powder at a temperature of 1100 ° C. for 1 hour under an argon atmosphere, it was cooled to room temperature, 1 liter of distilled water was added, and the powder was further dispersed for 1 hour by ultrasonication to prepare a suspension. . To this was added 0.1 liter of 5% hydrofluoric acid (HF) and ultrasonic waves were applied for 30 minutes to dissolve and remove the silicon oxide. Thereafter, the suspension was filtered and washed using a membrane filter to separate the product and dried to obtain a silicon powder.
この粉末の主成分はＳｉであり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量は５ｐｐｍであることを化学分析により確認した。さらに透過型電子顕微鏡（ＴＥＭ）で粉末に含まれる粒子の粒径を測定したところ、１０〜４０ｎｍであった。 The main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and Cl was 5 ppm. Furthermore, when the particle size of the particles contained in the powder was measured with a transmission electron microscope (TEM), it was 10 to 40 nm.
＜実施例２＞
モノシランガス０．０８Ｌ／ｍｉｎ、酸素ガス０．０４４Ｌ／ｍｉｎ及び希釈用のアルゴンガス１８Ｌ／ｍｉｎを、温度７５０℃、圧力５０ｋＰａに保持した実施例１と同じ石英ガラス製反応管からなる反応容器に導入したところ、茶褐色の粉末が生成した。これを実施例１と同様にして捕集した。
<Example 2>
Monosilane gas 0.08 L / min, oxygen gas 0.044 L / min, and argon gas 18 L / min for dilution were introduced into a reaction vessel composed of the same quartz glass reaction tube as in Example 1 maintained at a temperature of 750 ° C. and a pressure of 50 kPa. As a result, a brown powder was produced. This was collected in the same manner as in Example 1.
捕集した生成粉末の比表面積測定を行ったところ、１５０ｍ2／ｇであった。化学分析を行ったところ、主成分はＳｉ及び酸素、ＸＰＳのＳｉ2pスペクトルを調べた結果、Ｓｉ−Ｓｉ結合に帰属されるピークが認められ、生成物がシリコン粒子を内包したシリコン酸化物粒子であることを確認した。 It was 150 m < 2 > / g when the specific surface area measurement of the collected production | generation powder was performed. As a result of chemical analysis, Si and oxygen as main components and the Si 2p spectrum of XPS were examined. As a result, a peak attributed to the Si—Si bond was observed, and the product was silicon oxide particles containing silicon particles. I confirmed that there was.
この粉末２０ｇを、ヘリウム雰囲気下、９００℃の温度で１時間保持した以外は実施例１と同様にしてシリコン粉末を得た。この粉末の主成分はＳｉであり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量は８ｐｐｍであることを化学分析により確認した。さらにＴＥＭで粒子の粒径を測定したところ、２〜２４ｎｍであった。 A silicon powder was obtained in the same manner as in Example 1 except that 20 g of this powder was held at a temperature of 900 ° C. for 1 hour in a helium 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 Cl was 8 ppm. Furthermore, when the particle size of the particles was measured by TEM, it was 2 to 24 nm.
＜比較例１＞
Ｓｉを内包するシリコン酸化物粒子からなる粉末２０ｇを、アルゴン雰囲気下１４５０℃の温度で１時間保持した以外は、実施例１と同様にしてシリコン粉末を得た。
<Comparative Example 1>
A silicon powder was obtained in the same manner as in Example 1 except that 20 g of powder composed of silicon oxide particles containing Si was held at a temperature of 1450 ° C. for 1 hour in an argon atmosphere.
この粉末の主成分はＳｉであり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量は４ｐｐｍであることを化学分析により確認した。さらにＴＥＭで粒子の粒径を測定したところ、５０ｎｍを超える粒子１２質量％を含む、３５ｎｍ以上の粒子からなる粉末であった。 The main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and Cl was 4 ppm. Further, when the particle size of the particles was measured by TEM, it was a powder composed of particles of 35 nm or more containing 12% by mass of particles exceeding 50 nm.
＜比較例２＞
Ｓｉを内包するシリコン酸化物粒子からなる粉末２０ｇを、アルゴン雰囲気下７００℃の温度で１時間保持した以外は、実施例１と同様にしてシリコン粉末を得た。
<Comparative example 2>
A silicon powder was obtained in the same manner as in Example 1 except that 20 g of powder composed of silicon oxide particles containing Si was held at a temperature of 700 ° C. for 1 hour in an argon atmosphere.
この粉末の主成分はＳｉであり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量は１８ｐｐｍであることを化学分析により確認した。さらにＴＥＭで粒子の粒径を測定し、１ｎｍ未満の粒子１６質量％を含む、１０ｎｍ以下の粒子からなる粉末であった。 The main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and Cl was 18 ppm. Further, the particle diameter of the particles was measured by TEM, and the powder was composed of particles of 10 nm or less including 16% by mass of particles of less than 1 nm.
＜比較例３＞
Ｓｉを内包するシリコン酸化物粒子からなる粉末２０ｇを、ヘリウム雰囲気下７００℃の温度で１時間保持した以外は、実施例２と同様にしてシリコン粉末を得た。
<Comparative Example 3>
A silicon powder was obtained in the same manner as in Example 2 except that 20 g of powder composed of silicon oxide particles containing Si was held at a temperature of 700 ° C. for 1 hour in a helium atmosphere.
この粉末の主成分はＳｉであり、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量は２３ｐｐｍであることを化学分析により確認した。さらにＴＥＭで粒子の粒径を測定し、１ｎｍ未満の粒子４０質量％を含む、６ｎｍ以下の粒子からなる粉末であることを確認した。 The main component of this powder was Si, and it was confirmed by chemical analysis that the total amount of Na, Fe, Al, and Cl was 23 ppm. Further, the particle diameter of the particles was measured by TEM, and it was confirmed that the powder was composed of particles of 6 nm or less including 40% by mass of particles less than 1 nm.
＜比較例４＞
モノシランガスの代わりに、多結晶シリコンの原料として多用される四塩化珪素（ＳｉＣｌ4）ガスを用いた以外は実施例１と同様にして反応容器にガスを導入したところ、茶褐色の粉末を生成し、これを実施例１と同様にして捕集した。
<Comparative example 4>
When the gas was introduced into the reaction vessel in the same manner as in Example 1 except that silicon tetrachloride (SiCl 4 ) gas frequently used as a raw material for polycrystalline silicon was used instead of monosilane gas, a brown powder was produced. This was collected in the same manner as in Example 1.
捕集した生成粉末の比表面積測定を行ったところ４５ｍ2／ｇであった。化学分析を行ったところ、主成分はＳｉ及び酸素、ＸＰＳのＳｉ2pスペクトルを調べた結果、Ｓｉ−Ｓｉ結合に帰属されるピークが認められ、生成物がシリコン粒子を内包したシリコン酸化物粉末粒子であることを確認した。 It was 45 m < 2 > / g when the specific surface area measurement of the collected production | generation powder was performed. As a result of chemical analysis, the main components were Si and oxygen, and as a result of examining the Si 2p spectrum of XPS, a peak attributed to the Si—Si bond was observed, and the silicon oxide powder particles in which the product contained silicon particles It was confirmed that.
この粉末２０ｇを用い、実施例１と同様にしてシリコン粉末を得た。この粉末の主成分はＳｉであり、ＴＥＭで測定した粒子の粒径は５〜３５ｎｍであったが、特に塩素（Ｃｌ）を多く含み、Ｎａ，Ｆｅ，Ａｌ，Ｃｌの合計量は５０ｐｐｍであった。 Using 20 g of this powder, 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. In particular, the powder contained a large amount of chlorine (Cl), and the total amount of Na, Fe, Al, and Cl was 50 ppm. It was.
本発明によれば、特別な電解装置やプラズマ発生装置等を必要とせず高い生産性でナノメートルサイズのシリコン粒子からなる粉末を、工業的規模で大量に合成することが可能であり、これを原料粉末として用いることによって、新規で高性能な発光素子や電子部品等の機能性材料の実用化に寄与することができる。 According to the present invention, it is possible to synthesize a large amount of powder composed of nanometer-sized silicon particles on an industrial scale with high productivity without requiring a special electrolysis apparatus or plasma generation apparatus. By using it as a raw material powder, it can contribute to the practical application of functional materials such as new and high-performance light-emitting elements and electronic parts.
Claims (3)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004075521A JP4791697B2 (en) | 2004-03-17 | 2004-03-17 | Method for producing silicon particles |
| US10/592,864 US7850938B2 (en) | 2004-03-17 | 2005-02-18 | Silicon particles, silicon particle superlattice and method for producing the same |
| PCT/JP2005/002574 WO2005090234A1 (en) | 2004-03-17 | 2005-02-18 | Silicon particle, silicon particle superlattice and method for production thereof |
| CN2005800082566A CN1956920B (en) | 2004-03-17 | 2005-02-18 | Silicon particle, silicon particle superlattice and method for production thereof |
| US12/823,314 US8221881B2 (en) | 2004-03-17 | 2010-06-25 | Silicon particle, silicon particle superlattice and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004075521A JP4791697B2 (en) | 2004-03-17 | 2004-03-17 | Method for producing silicon particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005263522A true JP2005263522A (en) | 2005-09-29 |
| JP4791697B2 JP4791697B2 (en) | 2011-10-12 |
Family
ID=35088456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004075521A Expired - Fee Related JP4791697B2 (en) | 2004-03-17 | 2004-03-17 | Method for producing silicon particles |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4791697B2 (en) |
| CN (1) | CN1956920B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006024490A1 (en) * | 2006-05-26 | 2007-11-29 | Forschungszentrum Karlsruhe Gmbh | Suspension used in the production of a semiconductor for printed circuit boards contains a silicon dioxide layer arranged on silicon particles |
| WO2009069416A1 (en) * | 2007-11-29 | 2009-06-04 | Konica Minolta Medical & Graphic, Inc. | Semiconductor nanoparticle and method for producing the same |
| JP2013119489A (en) * | 2011-12-06 | 2013-06-17 | Bridgestone Corp | Method for manufacturing silicon fine particle |
| WO2014123331A1 (en) * | 2013-02-05 | 2014-08-14 | 주식회사 케이씨씨 | Method for continuously preparing silicon nanoparticles, and anode active material for lithium secondary battery comprising same |
| WO2016052643A1 (en) * | 2014-10-02 | 2016-04-07 | 山陽特殊製鋼株式会社 | Powder for conductive fillers |
| JP2016072192A (en) * | 2014-10-02 | 2016-05-09 | 山陽特殊製鋼株式会社 | Powder for electrical conductive filler |
| JP2016110773A (en) * | 2014-12-04 | 2016-06-20 | 山陽特殊製鋼株式会社 | Powder for conductive filler |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204507B (en) * | 2013-04-07 | 2018-03-06 | 李绍光 | A kind of Halogen silane thermal decomposition process for producing solar energy level silicon |
| CN104528727B (en) * | 2014-12-24 | 2016-08-24 | 东北大学 | A kind of porous silicon block materials with multistage directional hole and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0672705A (en) * | 1992-08-26 | 1994-03-15 | Ube Ind Ltd | Production of crystalline silicon superfine particle |
| JPH06279015A (en) * | 1993-03-30 | 1994-10-04 | Matsushita Electric Ind Co Ltd | Production of ultrafine silicon particle |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6585947B1 (en) * | 1999-10-22 | 2003-07-01 | The Board Of Trustess Of The University Of Illinois | Method for producing silicon nanoparticles |
-
2004
- 2004-03-17 JP JP2004075521A patent/JP4791697B2/en not_active Expired - Fee Related
-
2005
- 2005-02-18 CN CN2005800082566A patent/CN1956920B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0672705A (en) * | 1992-08-26 | 1994-03-15 | Ube Ind Ltd | Production of crystalline silicon superfine particle |
| JPH06279015A (en) * | 1993-03-30 | 1994-10-04 | Matsushita Electric Ind Co Ltd | Production of ultrafine silicon particle |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006024490A1 (en) * | 2006-05-26 | 2007-11-29 | Forschungszentrum Karlsruhe Gmbh | Suspension used in the production of a semiconductor for printed circuit boards contains a silicon dioxide layer arranged on silicon particles |
| WO2009069416A1 (en) * | 2007-11-29 | 2009-06-04 | Konica Minolta Medical & Graphic, Inc. | Semiconductor nanoparticle and method for producing the same |
| JP2013119489A (en) * | 2011-12-06 | 2013-06-17 | Bridgestone Corp | Method for manufacturing silicon fine particle |
| WO2014123331A1 (en) * | 2013-02-05 | 2014-08-14 | 주식회사 케이씨씨 | Method for continuously preparing silicon nanoparticles, and anode active material for lithium secondary battery comprising same |
| KR20140100122A (en) * | 2013-02-05 | 2014-08-14 | 주식회사 케이씨씨 | Continuous manufacturing method for silicon nanoparticles and anode active materials containing the same for lithium ion battery |
| KR101583216B1 (en) * | 2013-02-05 | 2016-01-07 | 주식회사 케이씨씨 | Continuous manufacturing method for silicon nanoparticles and anode active materials containing the same for lithium ion battery |
| WO2016052643A1 (en) * | 2014-10-02 | 2016-04-07 | 山陽特殊製鋼株式会社 | Powder for conductive fillers |
| JP2016072192A (en) * | 2014-10-02 | 2016-05-09 | 山陽特殊製鋼株式会社 | Powder for electrical conductive filler |
| JP2016110773A (en) * | 2014-12-04 | 2016-06-20 | 山陽特殊製鋼株式会社 | Powder for conductive filler |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1956920B (en) | 2012-03-07 |
| CN1956920A (en) | 2007-05-02 |
| JP4791697B2 (en) | 2011-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8221881B2 (en) | Silicon particle, silicon particle superlattice and method for producing the same | |
| US10023488B2 (en) | Synthetic amorphous silica powder and method for producing same | |
| JP5825145B2 (en) | Synthetic amorphous silica powder and method for producing the same | |
| JP5648640B2 (en) | Synthetic amorphous silica powder | |
| JP2007513041A (en) | Nanoscale crystalline silicon powder | |
| JP5724881B2 (en) | Synthetic amorphous silica powder and method for producing the same | |
| JP4791697B2 (en) | Method for producing silicon particles | |
| JPWO2018180901A1 (en) | Fibrous carbon nanostructure dispersion, method for producing the same, and fibrous carbon nanostructure | |
| WO2011083697A1 (en) | Synthetic amorphous silica powder and method for producing same | |
| JP2013532626A (en) | Silicon carbide and method for producing the same | |
| JP4556015B2 (en) | Zinc sulfide / silicon core / shell nanowire and method for producing the same | |
| JP3985044B2 (en) | Single crystal silicon nanotube and method for producing the same | |
| JP2007084369A (en) | TiC ULTRAFINE PARTICLE-SUPPORTED OR TiO2 ULTRAFINE PARTICLE-SUPPORTED CARBON NANOTUBE, TiC NANOTUBE, AND METHOD FOR PRODUCING THEM | |
| CN107598183B (en) | Macroscopic quantity preparation method of nano-silver particles | |
| CN107473228A (en) | A kind of nanoscale crystalline silicon and preparation method thereof | |
| JP5962219B2 (en) | Synthetic amorphous silica powder and method for producing the same | |
| CN107934946B (en) | Graphene powder and preparation method thereof | |
| WO2008071504A2 (en) | Porous silicon | |
| JP2004161507A (en) | Silicon carbide nanorod and its production process | |
| WO2021049557A1 (en) | Method for producing purified silicon fine particles | |
| JP4756239B2 (en) | Hollow spherical particles made of gallium nitride and method for producing the same | |
| JP4576603B2 (en) | Method for producing indium phosphide nanotubes | |
| KR101796076B1 (en) | Process for the preparation of hydrophobic silicon particles and hydrophobic silicon particles produced therefrom | |
| JP2013203641A (en) | Synthetic amorphous silica powder and production method therefor | |
| Wang et al. | Characterization of ZnO nanorods grown on Si substrates coated with NiCl2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070208 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20070208 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100622 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100823 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110712 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110722 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140729 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4791697 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140729 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140729 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |