JP4572382B2 - Single crystal silicon nitride nanosheet and manufacturing method thereof - Google Patents
Single crystal silicon nitride nanosheet and manufacturing method thereof Download PDFInfo
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- JP4572382B2 JP4572382B2 JP2004352353A JP2004352353A JP4572382B2 JP 4572382 B2 JP4572382 B2 JP 4572382B2 JP 2004352353 A JP2004352353 A JP 2004352353A JP 2004352353 A JP2004352353 A JP 2004352353A JP 4572382 B2 JP4572382 B2 JP 4572382B2
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Description
本発明は、ケイ素粉末を原料とした単結晶窒化ケイ素ナノシートとその製造方法に関するものである。 The present invention relates to a single crystal silicon nitride nanosheet using silicon powder as a raw material and a method for producing the same.
セラミックスのナノシートは酸化チタンをはじめ、いくつかの報告例がある。しかしながら、これらは層状物質からの剥離により合成するものであり、本発明のように気相法によるナノシートの報告例は、とても少ない。一方、窒化ケイ素のナノ構造体として、様々な原料、雰囲気及び熱処理方法により、ナノサイズの単結晶ナノロッドやナノウィイスカーが合成されてきた。しかしながら、これまでに上述の一次元ナノ構造体であるナノロッド及びナノウィスカーの合成の報告は多数存在するが、二次元構造体であるナノシートの報告例はない。 Ceramic nanosheets include titanium oxide and some other reported examples. However, these are synthesized by peeling from the layered material, and there are very few reports of nanosheets by the vapor phase method as in the present invention. On the other hand, nano-sized single crystal nanorods and nanowhiskers have been synthesized as silicon nitride nanostructures by various raw materials, atmospheres, and heat treatment methods. However, there have been many reports on the synthesis of nanorods and nanowhiskers that are the above-described one-dimensional nanostructures, but there are no reports on nanosheets that are two-dimensional structures.
従って、本発明は、単結晶窒化ケイ素ナノシートを提供することを目的とする。
また、本発明は、単結晶窒化ケイ素ナノシートを製造するための方法であって、簡便に生産が可能な方法を提供することを目的とする。
Accordingly, an object of the present invention is to provide a single crystal silicon nitride nanosheet.
Another object of the present invention is to provide a method for producing a single crystal silicon nitride nanosheet, which can be easily produced.
上記従来技術の問題点を解決するため、本発明者らは鋭意研究を行った結果、原料としてケイ素粉末を用いて、所定の温度及び窒素ガス流量の条件下で反応させることにより、簡便な処理で、単結晶窒化ケイ素ナノシートを製造できることを発見し、本発明を完成させた。 In order to solve the above-described problems of the prior art, the present inventors have conducted intensive research, and as a result, by using silicon powder as a raw material and reacting under conditions of a predetermined temperature and a nitrogen gas flow rate, a simple treatment is possible. Thus, it was discovered that single crystal silicon nitride nanosheets can be produced, and the present invention has been completed.
要するに、本発明は、単結晶窒化ケイ素ナノシートを製造するための方法であって、原料としてケイ素粉末を用い、ケイ素粉末の窒化反応が進行する温度以上であり、且つケイ素粉末が溶融しない温度以下の温度で窒素と反応させることを特徴とするものである。 In short, the present invention is a method for producing single-crystal silicon nitride nanosheets, using silicon powder as a raw material, at or above the temperature at which the nitriding reaction of silicon powder proceeds and below the temperature at which silicon powder does not melt It is characterized by reacting with nitrogen at a temperature.
また、本発明は、単結晶窒化ケイ素ナノシートを製造するための方法であって、原料としてケイ素粉末を用い、非密封状態の容器中に入れ、窒素ガス流量を電気炉内断面積が25cm2あたり0.5 l/min以上の条件で、1300℃〜1400℃の温度で反応させることを特徴とするものである。 Further, the present invention is a method for producing a single crystal silicon nitride nanosheet, using silicon powder as a raw material, put in a non-sealed container, the nitrogen gas flow rate per electric furnace cross-sectional area 25cm 2 The reaction is performed at a temperature of 1300 ° C. to 1400 ° C. under a condition of 0.5 l / min or more.
また、本発明は、単結晶窒化ケイ素ナノシートであって、大きさが1μｍ×1μｍ以上で厚みが20nm以下であることを特徴とするものである。 In addition, the present invention is a single crystal silicon nitride nanosheet having a size of 1 μm × 1 μm or more and a thickness of 20 nm or less.
本発明に従えば、これまでに報告されていないナノサイズの二次元構造を有する単結晶窒化ケイ素ナノシートを、簡便に製造することが可能となる。
即ち、本発明により、容易に入手できるケイ素粉末を使用し、且つ反応装置の構造及び反応操作が簡単な気相法を使用することにより、大きさが1μｍ×1μｍ以上で厚みが20nm以下である単結晶窒化ケイ素ナノシートを製造することができる。
According to the present invention, a single crystal silicon nitride nanosheet having a nano-sized two-dimensional structure that has not been reported so far can be easily produced.
That is, according to the present invention, by using a readily available silicon powder and using a gas phase method with a simple reactor structure and reaction operation, the size is 1 μm × 1 μm or more and the thickness is 20 nm or less. Single crystal silicon nitride nanosheets can be produced.
本発明の明細書中において「単結晶窒化ケイ素ナノシート」とは、大きさが1μｍ×1μｍ以上で厚みが20nm以下である単結晶の窒化ケイ素ナノシートを表す。
本発明の単結晶窒化ケイ素ナノシートは、以下の手順で製造することができる。
In the specification of the present invention, the “single crystal silicon nitride nanosheet” represents a single crystal silicon nitride nanosheet having a size of 1 μm × 1 μm or more and a thickness of 20 nm or less.
The single crystal silicon nitride nanosheet of the present invention can be produced by the following procedure.
まず、ケイ素粉末を原料とし、これらを非密封状態の容器中におく。容器は1400℃程度の温度に耐えうるものであれば制限はないが、好ましくは、坩堝である。坩堝は処理条件において原料と反応しない材質のものであればよく、好ましくは、窒化ボロン製坩堝である。 First, silicon powder is used as a raw material, and these are placed in an unsealed container. The container is not limited as long as it can withstand a temperature of about 1400 ° C., but is preferably a crucible. The crucible may be of a material that does not react with the raw material under the processing conditions, and is preferably a boron nitride crucible.
本発明において使用することができるケイ素粉末は特に制限はない。
次いで、非密封状態の坩堝を電気炉内に配置し、電気炉内を一度真空（10-2Pa程度の真空度）にしてから窒素ガスで大気圧に戻し、電気炉等の適当な手段により1300℃〜1400℃の温度に加熱し、その後電気炉内断面積が25cm2あたり0.5 l/min以上の流量の窒素ガスと約30時間反応させてケイ素粉末原料から窒化ケイ素を生成させる。このとき、温度は、窒化ケイ素生成反応が進行する1300℃以上で、ケイ素が溶融しない1400℃以下の温度に設定することを要する。
The silicon powder that can be used in the present invention is not particularly limited.
Next, an unsealed crucible is placed in the electric furnace, and once the inside of the electric furnace is evacuated (vacuum degree of about 10 −2 Pa), it is returned to atmospheric pressure with nitrogen gas, and by an appropriate means such as an electric furnace. It is heated to a temperature of 1300 ° C. to 1400 ° C., and then reacted with nitrogen gas at a flow rate of 0.5 l / min or more per 25 cm 2 in an electric furnace to generate silicon nitride from the silicon powder raw material. At this time, the temperature needs to be set to a temperature of 1300 ° C. or higher at which the silicon nitride formation reaction proceeds and 1400 ° C. or lower at which silicon does not melt.
このようにして製造される本発明の単結晶窒化ケイ素ナノシートは、大きさが1μｍ×１μｍ以上で、厚みが20nm以下であるナノシートである。
以下、本発明を、一実施態様である実施例によって更に詳細に説明するが、本発明はこの実施例に限定されるものではない。
The single crystal silicon nitride nanosheet of the present invention thus produced is a nanosheet having a size of 1 μm × 1 μm or more and a thickness of 20 nm or less.
Hereinafter, the present invention will be described in more detail with reference to an example which is one embodiment, but the present invention is not limited to this example.
（実施例１）
本発明の単結晶窒化ケイ素ナノシートの製造方法を実施するのに使用することができる装置の一例を、図１に示す。
Example 1
An example of an apparatus that can be used to carry out the method for producing a single crystal silicon nitride nanosheet of the present invention is shown in FIG.
図１において、原料であるケイ素粉末1を、窒化ボロン製の坩堝2中に入れた。本実施例において、ケイ素粉末は、ニラコ社製のケイ素粉末を使用した（粒度200〜300メッシュ、純度99.999%）。 In FIG. 1, silicon powder 1 as a raw material was placed in a crucible 2 made of boron nitride. In this example, silicon powder manufactured by Niraco was used as the silicon powder (particle size 200-300 mesh, purity 99.999%).
その上から、窒化ボロン製の蓋3で坩堝に蓋をし、その坩堝を電気炉容器（真空容器）4に入れた。電気炉容器中を一度10-2Pa程度まで真空排気し、窒素ガスで大気圧に戻し、電気炉内断面積が25cm2あたり0.75 l/minの流量の窒素ガスを流し、ヒーター5で1400℃にした後、30時間坩堝を電気炉容器中に静置し、ケイ素粉末と窒素ガスを反応させた。 Then, the crucible was covered with a lid 3 made of boron nitride, and the crucible was put into an electric furnace vessel (vacuum vessel) 4. The electric furnace vessel is once evacuated to about 10 -2 Pa, returned to atmospheric pressure with nitrogen gas, nitrogen gas at a flow rate of 0.75 l / min per 25 cm 2 in the electric furnace cross section, and 1400 ° C with heater 5 After that, the crucible was left in an electric furnace vessel for 30 hours to react silicon powder with nitrogen gas.
製造された単結晶窒化ケイ素ナノシートの透過型電子顕微鏡写真及び電子線回折パターンを、図2に示す。図より、本発明の方法に従えば、大きさが1μｍ×１μｍ以上で、厚みが20nm以下である単結晶窒化ケイ素ナノシートを粉末表面に形成することができる。即ち、その形成されたシートは、図２の左図の矢印で示される長方形の影のような部分であり、その大きさは1μｍ×１μｍ以上である。又、図２の右図の（ａ）、（ｂ）、（ｃ）及び（ｄ）は、図２の左図に示される単結晶窒化ケイ素ナノシートの（ａ）、（ｂ）、（ｃ）及び（ｄ）箇所における格子像の拡大図である。 FIG. 2 shows a transmission electron micrograph and an electron diffraction pattern of the produced single crystal silicon nitride nanosheet. From the figure, according to the method of the present invention, single crystal silicon nitride nanosheets having a size of 1 μm × 1 μm or more and a thickness of 20 nm or less can be formed on the powder surface. That is, the formed sheet is a rectangular shadow portion indicated by an arrow in the left diagram of FIG. 2 and has a size of 1 μm × 1 μm or more. 2 (a), (b), (c) and (d) are (a), (b) and (c) of the single crystal silicon nitride nanosheet shown in the left diagram of FIG. And (d) is an enlarged view of a lattice image at a location.
（比較例）
実施例と同様な方法で、ケイ素粉末を電気炉中に入れ、真空排気した後、電気炉内断面積が25cm2あたり0.2 l/minの流量の窒素ガスを流し、1300℃で30時間反応させた。これにより、作製された試料の電子顕微鏡写真を図3に示す。図より、二次元方向に広がりを有さない、一次元の単結晶窒化ケイ素ナノロッド及びナノベルトが形成されていることがわかった。即ち、窒素ガスの流量が0.2 ｌ／ｍｉｎではシート状の単結晶窒化ケイ素が生成しないことを示している。
(Comparative example)
In the same manner as in the examples, silicon powder was put in an electric furnace and evacuated, and then the cross-sectional area in the electric furnace was made to flow at a flow rate of 0.2 l / min per 25 cm 2 and reacted at 1300 ° C. for 30 hours. It was. An electron micrograph of the sample thus prepared is shown in FIG. From the figure, it was found that one-dimensional single-crystal silicon nitride nanorods and nanobelts having no extension in the two-dimensional direction were formed. That is, when the flow rate of nitrogen gas is 0.2 l / min, sheet-like single crystal silicon nitride is not generated.
従来窒化アルミニウムなどの絶縁体が、パワー半導体モジュールの絶縁基板として用いられていた。近年、高強度、高熱伝導率である窒化ケイ素を用いて、モジュール構造の簡略化を行なってきた。さらに、ナノメートルオーダーととても薄い、本発明の窒化ケイ素ナノシートを用いることにより、これらモジュールの小型化を図れる可能性がある。 Conventionally, an insulator such as aluminum nitride has been used as an insulating substrate of a power semiconductor module. In recent years, module structures have been simplified using silicon nitride having high strength and high thermal conductivity. Further, by using the silicon nitride nanosheet of the present invention, which is very thin on the order of nanometers, there is a possibility that these modules can be miniaturized.
１ ケイ素粉末
２ 窒化ボロン製坩堝
３ 窒化ボロン製坩堝の蓋
４ 電気炉容器（真空容器）
５ ヒーター
1 Silicon powder 2 Boron nitride crucible 3 Boron nitride crucible lid 4 Electric furnace vessel (vacuum vessel)
5 Heater
Claims (2)
The method of claim 1, wherein the unsealed container is a boron nitride crucible .
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| JPS4927755B1 (en) * | 1970-08-18 | 1974-07-20 | ||
| JPS5550882B2 (en) * | 1973-03-27 | 1980-12-20 | ||
| JPS61266305A (en) * | 1985-05-17 | 1986-11-26 | Onoda Cement Co Ltd | Production of silicon nitride |
| JPS63151603A (en) * | 1986-12-12 | 1988-06-24 | Shin Etsu Chem Co Ltd | Production of silicon nitride powder |
| JPH01201012A (en) * | 1987-10-02 | 1989-08-14 | Japan Metals & Chem Co Ltd | Production of silicon nitride powder |
| CA2003811C (en) * | 1988-12-08 | 1997-01-14 | Jochen Hintermayer | Production of silicon nitride and the product thereby obtained |
| JP3061845B2 (en) * | 1990-09-28 | 2000-07-10 | 株式会社東芝 | Method for producing inorganic compound thin film |
| JPH10218612A (en) * | 1997-02-03 | 1998-08-18 | Shin Etsu Chem Co Ltd | Method for producing silicon nitride powder |
| JPH10310500A (en) * | 1997-05-01 | 1998-11-24 | Okura Ind Co Ltd | Shape control method of silicon nitride whiskers |
| JP3698664B2 (en) * | 2001-10-03 | 2005-09-21 | 電気化学工業株式会社 | Method for producing high purity silicon nitride powder |
| JP4000371B2 (en) * | 2003-01-29 | 2007-10-31 | 独立行政法人物質・材料研究機構 | Silicon nitride (Si3N4) nanorods and manufacturing method thereof |
| JP3918060B2 (en) * | 2003-07-30 | 2007-05-23 | 独立行政法人物質・材料研究機構 | Method for producing single crystal α-type silicon nitride nanoribbon |
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