JP4581121B2 - Silicon nitride nanowire coated with boron nitride nanosheet and method for producing the same - Google Patents
Silicon nitride nanowire coated with boron nitride nanosheet and method for producing the same Download PDFInfo
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本発明は、優れた電界放出特性を有し、ディスプレイ装置の冷陰極等に利用可能な、窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤー及びその製造方法に関する。 The present invention relates to a silicon nitride nanowire coated with a boron nitride nanosheet that has excellent field emission characteristics and can be used for a cold cathode of a display device, and a method for manufacturing the same.
カーボンナノチューブなどのように、ナノメートルサイズに材料を微小化すると、その曲率半径が小さくなることで、同じ重量当たりの角部の数が増加するため、放射中心が増加し、優れた電界放射特性を示すようになる（例えば、非特許文献１〜４参照）。
窒化ホウ素（ＢＮ）はバンドギャップ（六方晶では５．５ｅＶ、立方晶では約６．４ｅＶ）が広く、化学的に不活性で、熱安定性及び熱伝導性の優れた材料であり、電子放出材料として有望である（例えば、非特許文献５，６参照）。また、窒化ホウ素は、ナノチューブ、ナノワイヤー、ナノコーン、ナノケーブル、樹状構造物等の色々な形状が知られている（例えば、非特許文献７〜１２参照）。
一方、窒化珪素（Ｓｉ3 Ｎ4 ）は、機械的及び熱的性質の優れた材料であり、信頼性の高い基板材料への応用が有望視されている。
When a material is reduced to a nanometer size, such as carbon nanotubes, the radius of curvature decreases, so the number of corners per weight increases, resulting in an increase in emission center and excellent field emission characteristics. (For example, see Non-Patent Documents 1 to 4).
Boron nitride (BN) has a wide band gap (5.5 eV for hexagonal crystals, approximately 6.4 eV for cubic crystals), is chemically inert, has excellent thermal stability and thermal conductivity, and emits electrons. It is promising as a material (for example, see Non-Patent Documents 5 and 6). Boron nitride is known in various shapes such as nanotubes, nanowires, nanocones, nanocables, and dendritic structures (for example, see Non-Patent Documents 7 to 12).
On the other hand, silicon nitride (Si 3 N 4 ) is a material having excellent mechanical and thermal properties, and is expected to be applied to a highly reliable substrate material.
このようなカーボンや窒化ホウ素のナノチューブなどのナノ構造物をディスプレイの電界電子放出電極、所謂冷陰極として用いる場合には、これらのナノチューブを陰極となる基板に配置する必要がある。そして、所定の陰極面積においてその密度を一定にするなどの加工技術が要求される。
しかしながら、重量当たりの角部の数を多くできる窒化ホウ素のナノシートを、基板となる窒化珪素などのナノワイヤーに被覆することができないという課題を有している。
When such a nanostructure such as a carbon or boron nitride nanotube is used as a field electron emission electrode of a display, that is, a so-called cold cathode, it is necessary to dispose these nanotubes on a substrate serving as a cathode. A processing technique such as making the density constant in a predetermined cathode area is required.
However, there is a problem that a boron nitride nanosheet capable of increasing the number of corners per weight cannot be coated on a nanowire such as silicon nitride serving as a substrate.
本発明は上記課題に鑑み、化学的に不活性で、すなわち、化学的安定性が高く、かつ、電子放出材料として使用できる窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤー及びその製造方法を提供することを目的とする。 In view of the above problems, the present invention provides a silicon nitride nanowire coated with a boron nitride nanosheet that is chemically inert, that is, has high chemical stability and can be used as an electron emission material, and a method for producing the same. For the purpose.
上記目的を達成するために、本発明の窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーは、α型六方晶系窒化珪素ナノワイヤーが、六方晶系窒化ホウ素ナノシートで被覆されていることを特徴とする。
この構成によれば、α型六方晶系窒化珪素ナノワイヤー上の六方晶系窒化ホウ素ナノシートはナノサイズであるので、角部の数が増加するため放射中心が増加し、優れた電界放射特性を示し、ディスプレイや電子ビーム露光装置の冷陰極材料として使用できる。また、六方晶系窒化ホウ素ナノシートは、窒化珪素ナノワイヤーの表面に成長しているので、化学的安定性が極めて高い。
In order to achieve the above object, the silicon nitride nanowire coated with the boron nitride nanosheet of the present invention is characterized in that the α-type hexagonal silicon nitride nanowire is coated with a hexagonal boron nitride nanosheet. To do.
According to this configuration, since the hexagonal boron nitride nanosheet on the α-type hexagonal silicon nitride nanowire is nano-sized, the number of corners increases, the number of radiation centers increases, and excellent field emission characteristics are achieved. It can be used as a cold cathode material for a display or an electron beam exposure apparatus. Moreover, since the hexagonal boron nitride nanosheet is grown on the surface of the silicon nitride nanowire, the chemical stability is extremely high.
本発明の窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーの製造方法は、窒素ガス雰囲気中で珪素粉末を加熱することにより窒化珪素ナノワイヤーを合成し、次に、窒素ガス及びアンモニアガスの混合ガス雰囲気中で、ホウ素と窒素と酸素とから成る化合物（以下、適宜、Ｂ−Ｎ−Ｏ化合物と呼ぶ）及び酸化ホウ素の混合物を加熱することによって、窒化珪素ナノワイヤーを窒化ホウ素ナノシートで被覆することを特徴とする。
具体的には、加熱炉に、それぞれ、珪素を入れた坩堝と、Ｂ−Ｎ−Ｏ化合物及び酸化ホウ素の混合物を入れた坩堝とを配置し、窒素ガスを流しながら、珪素を１３５０〜１５５０℃の温度範囲で加熱して窒化珪素ナノワイヤーを合成し、次に、窒素ガス及びアンモニアガスの混合ガス雰囲気中で、Ｂ−Ｎ−Ｏ化合物及び酸化ホウ素の混合物を１４００〜１８００℃の温度範囲で加熱することによって、窒化珪素ナノワイヤーを窒化ホウ素ナノシートで被覆する。
上記方法において、混合物中のＢ−Ｎ−Ｏ化合物と酸化ホウ素粉末との重量比は、好ましくは、８０：２０〜９５：５の範囲である。
混合物と珪素粉末との重量比は、好ましくは、３：１〜１：２の範囲である。珪素の加熱時間は、好ましくは、３０分以上６０分以下である。Ｂ−Ｎ−Ｏ化合物及び酸化ホウ素の混合物の加熱時間は、好ましくは、３０分以上９０分以下である。
珪素の加熱時に流す窒素ガスの流量は、好ましくは、０．５リットル／分以上１．５リットル／分以下である。
また、混合ガスにおいて、好ましくは、窒素ガスの流量は１リットル／分以上２リットル／分以下であり、アンモニアガスの流量は０．０２リットル／分以上０．２リットル／分以下である。
この方法によれば、珪素を窒化して窒化珪素ナノワイヤーを合成し、この表面に窒化ホウ素ナノ構造物が成長する。この窒化ホウ素ナノ構造物は、結晶性六方晶系窒化ホウ素ナノシートである。
The method for producing silicon nitride nanowires coated with boron nitride nanosheets of the present invention synthesizes silicon nitride nanowires by heating silicon powder in a nitrogen gas atmosphere, and then a mixed gas of nitrogen gas and ammonia gas Coating silicon nitride nanowires with boron nitride nanosheets by heating a mixture of boron oxide, nitrogen compound and oxygen compound (hereinafter referred to as B—N—O compound) and boron oxide in an atmosphere. It is characterized by.
Specifically, a crucible containing silicon and a crucible containing a mixture of a B—N—O compound and boron oxide are arranged in a heating furnace, respectively, and silicon is flowed from 1350 to 1550 ° C. while flowing nitrogen gas. Next, a silicon nitride nanowire is synthesized by heating in a temperature range of 1 to 1800 ° C. in a mixed gas atmosphere of nitrogen gas and ammonia gas. By heating, silicon nitride nanowires are coated with boron nitride nanosheets.
In the above method, the weight ratio of the B—N—O compound to the boron oxide powder in the mixture is preferably in the range of 80:20 to 95: 5.
The weight ratio of the mixture to the silicon powder is preferably in the range of 3: 1 to 1: 2. The heating time of silicon is preferably 30 minutes or longer and 60 minutes or shorter. The heating time of the mixture of the B—N—O compound and boron oxide is preferably 30 minutes or longer and 90 minutes or shorter.
The flow rate of nitrogen gas that flows when silicon is heated is preferably 0.5 liters / minute or more and 1.5 liters / minute or less.
In the mixed gas, the flow rate of nitrogen gas is preferably 1 liter / minute or more and 2 liter / minute or less, and the flow rate of ammonia gas is 0.02 liter / minute or more and 0.2 liter / minute or less.
According to this method, silicon nitride is nitrided to synthesize silicon nitride nanowires, and boron nitride nanostructures grow on this surface. This boron nitride nanostructure is a crystalline hexagonal boron nitride nanosheet.
本発明の窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤー及びその製造方法によれば、α型六方晶系窒化珪素ナノワイヤー上の六方晶系窒化ホウ素ナノシートはナノサイズであるので、角部の数が増加するため放射中心が増加する。したがって、この窒化珪素ナノワイヤー上の窒化ホウ素ナノシートをディスプレイや電子ビーム露光装置の冷陰極に用いれば、優れた電界放射特性が得られる。また、窒化ホウ素は六方晶系窒化ホウ素ナノシートであり、窒化珪素ナノワイヤーの表面に成長しているので、化学的安定性が極め
て高い。
According to the silicon nitride nanowire coated with the boron nitride nanosheet of the present invention and the manufacturing method thereof, since the hexagonal boron nitride nanosheet on the α-type hexagonal silicon nitride nanowire is nano-sized, the number of corners Increases the radiation center. Therefore, if the boron nitride nanosheet on the silicon nitride nanowire is used for a cold cathode of a display or an electron beam exposure apparatus, excellent field emission characteristics can be obtained. Further, boron nitride is a hexagonal boron nitride nanosheet and grows on the surface of silicon nitride nanowires, so that the chemical stability is extremely high.
以下、本発明を実施するための最良の形態を図面に基づき詳細に説明する。
図１は、本発明の窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーを製造する装置の一例を示す模式図である。この装置を例に製造方法を説明する。
図において、縦型高周波誘導加熱装置１は、反応管２の周囲に、上部誘導加熱コイル３及び下部誘導加熱コイル４を有している。そして、珪素粉末５を入れた第１の坩堝６と、Ｂ−Ｎ−Ｏ化合物と酸化ホウ素との混合物７を入れた第２の坩堝８とを、それぞれ、反応管２の上部及び下部に配置している。
第１の坩堝６及び第２の坩堝８が、それぞれ、上部誘導加熱コイル３及び下部誘導加熱コイル４で加熱される。矢印９はＢ−Ｎ−Ｏ化合物蒸気を表している。また、矢印１０は反応管２に供給される、窒素ガス、または、窒素ガス及びアンモニアガスの混合ガスを表している。
ここで、加熱装置には、高周波誘導加熱法を利用した高周波誘導加熱炉を用いるのが好ましいが、この場合、縦型に限らず横型でもよい。また、加熱装置は、高周波誘導加熱に限らず、坩堝７，８を所定の温度に加熱できるランプ加熱や抵抗加熱による加熱装置でもよい。
Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic view showing an example of an apparatus for producing silicon nitride nanowires coated with the boron nitride nanosheet of the present invention. A manufacturing method will be described using this apparatus as an example.
In the figure, a vertical high frequency induction heating apparatus 1 has an upper induction heating coil 3 and a lower induction heating coil 4 around a reaction tube 2. Then, a first crucible 6 containing silicon powder 5 and a second crucible 8 containing a mixture 7 of a B—N—O compound and boron oxide are disposed at the upper and lower portions of the reaction tube 2, respectively. is doing.
The first crucible 6 and the second crucible 8 are heated by the upper induction heating coil 3 and the lower induction heating coil 4, respectively. Arrow 9 represents the B—N—O compound vapor. An arrow 10 represents nitrogen gas or a mixed gas of nitrogen gas and ammonia gas supplied to the reaction tube 2.
Here, it is preferable to use a high-frequency induction heating furnace using a high-frequency induction heating method as the heating device, but in this case, not only a vertical type but also a horizontal type may be used. The heating device is not limited to high-frequency induction heating, and may be a heating device using lamp heating or resistance heating that can heat the crucibles 7 and 8 to a predetermined temperature.
図１の装置を用いて窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーを製造する方法を説明する。
初めに、Ｂ−Ｎ−Ｏ化合物粉末を作製しておく。Ｂ−Ｎ−Ｏ化合物の粉末は、例えば、後に詳細に説明するように、ホウ酸とメラミンから合成できる。
珪素粉末５と、Ｂ−Ｎ−Ｏ化合物粉末及び酸化ホウ素粉末の混合物７と、を図１に示したように配置する。最初に、窒素ガス１０を流し、上部誘導加熱コイル３で珪素粉末５を加熱して、窒化珪素ナノワイヤーを合成する。
次に、下部誘導加熱コイル４でＢ−Ｎ−Ｏ化合物粉末及び酸化ホウ素粉末の混合物７を加熱してホウ素、酸素、窒素からなる化合物蒸気（以下、適宜、Ｂ−Ｎ−Ｏ化合物蒸気と呼ぶ）９を生成し、かつ、窒素ガスとアンモニアガスの混合ガス１０を流す。一定時間この状態を保持し、窒化珪素ナノワイヤー上に窒化ホウ素ナノシートを堆積させることで、窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーを得る。
A method for producing silicon nitride nanowires coated with boron nitride nanosheets using the apparatus of FIG. 1 will be described.
First, a B—N—O compound powder is prepared. The powder of the B—N—O compound can be synthesized from boric acid and melamine, for example, as will be described in detail later.
The silicon powder 5 and the mixture 7 of the B—N—O compound powder and the boron oxide powder are arranged as shown in FIG. First, nitrogen gas 10 is flowed and the silicon powder 5 is heated by the upper induction heating coil 3 to synthesize silicon nitride nanowires.
Next, the mixture 7 of the B—N—O compound powder and the boron oxide powder is heated by the lower induction heating coil 4, and a compound vapor composed of boron, oxygen, and nitrogen (hereinafter referred to as “B—N—O compound vapor” as appropriate). ) 9 and a mixed gas 10 of nitrogen gas and ammonia gas is allowed to flow. By maintaining this state for a certain period of time and depositing boron nitride nanosheets on the silicon nitride nanowires, silicon nitride nanowires coated with the boron nitride nanosheets are obtained.
最初の窒化珪素ナノワイヤーの合成温度は１３５０℃〜１５５０℃の範囲が好ましく、１５５０℃で十分であり、これ以上の温度ではＢ−Ｎ−Ｏ化合物粉末の蒸発も起こる可能性があり、好ましくない。
また、このときの加熱時間は０．５時間〜１．０時間の範囲が好ましく、１時間で十分に反応が進行するので、これ以上の時間をかける必要はない。０．５時間未満では収量が低下する。
さらに、このときの窒素ガスの流量は毎分０．５〜２リットルの範囲が好ましく、２リットル／分以上の流量では生成物が坩堝外へ吹き飛ばされてしまうので好ましくない。そして、０．５リットル／分未満の流量では窒化珪素ナノワイヤーを十分に形成することができない。
The synthesis temperature of the first silicon nitride nanowire is preferably in the range of 1350 ° C. to 1550 ° C., and 1550 ° C. is sufficient. At temperatures higher than this, evaporation of the B—N—O compound powder may occur, which is not preferable. .
In addition, the heating time at this time is preferably in the range of 0.5 hour to 1.0 hour, and the reaction proceeds sufficiently in 1 hour, so that it is not necessary to spend more time. In less than 0.5 hour, the yield decreases.
Furthermore, the flow rate of nitrogen gas at this time is preferably in the range of 0.5 to 2 liters per minute, and a flow rate of 2 liters / minute or more is not preferable because the product is blown out of the crucible. And silicon nitride nanowire cannot fully be formed with the flow volume of less than 0.5 liter / min.
窒化珪素ナノワイヤー上に窒化ホウ素ナノシートを被覆する次の段階の加熱温度は１４００℃〜１８００℃の範囲が好ましく、１８００℃で十分に蒸発と反応が進行するので、これ以上の温度にする必要はない。また、１４００℃未満の温度では窒化ホウ素ナノシート形成のためのＢ−Ｎ−Ｏ化合物粉末が十分に蒸発しない。
このときの加熱時間は０．５時間〜１．５時間の範囲が好ましく、１．５時間で十分に反応が進行するので、これ以上の時間をかける必要はない。また、０．５時間未満の加熱時間では窒化ホウ素ナノシートの収量が低下する。
また、窒素ガスの流量は１〜２リットル／分の範囲が好ましく、２リットル／分以上の流量では生成物が散逸してしまう。１リットル／分未満の流量では窒化ホウ素ナノシートの収量が低下する。
さらに、アンモニアガスの流量は０．０２リットル／分〜０．２リットル／分の範囲が好ましく、０．２リットル／分以上の流量では非晶質の窒化ホウ素になり、０．０２リットル／分未満の流量では窒化ホウ素ナノシートの収量が低下する。
The heating temperature of the next step of coating the boron nitride nanosheet on the silicon nitride nanowire is preferably in the range of 1400 ° C to 1800 ° C, and the evaporation and reaction proceed sufficiently at 1800 ° C. Absent. Further, at a temperature lower than 1400 ° C., the B—N—O compound powder for forming boron nitride nanosheets does not evaporate sufficiently.
The heating time at this time is preferably in the range of 0.5 to 1.5 hours, and since the reaction proceeds sufficiently in 1.5 hours, it is not necessary to spend more time. In addition, when the heating time is less than 0.5 hours, the yield of boron nitride nanosheets decreases.
The flow rate of nitrogen gas is preferably in the range of 1 to 2 liters / minute, and the product is dissipated at a flow rate of 2 liters / minute or more. At a flow rate of less than 1 liter / min, the yield of boron nitride nanosheets decreases.
Further, the flow rate of ammonia gas is preferably in the range of 0.02 liters / minute to 0.2 liters / minute. At a flow rate of 0.2 liters / minute or more, amorphous boron nitride is formed, and 0.02 liters / minute is obtained. If the flow rate is less than that, the yield of boron nitride nanosheets decreases.
上記の操作において、混合物７中のＢ−Ｎ−Ｏ化合物粉末と酸化ホウ素粉末との重量比は８０：２０〜９５：５の範囲が好ましい。
Ｂ−Ｎ−Ｏ化合物粉末の重量がこの範囲よりも多いと、目的の窒化ホウ素ナノシートが得られず、ナノチューブやナノ粒子が生成する。Ｂ−Ｎ−Ｏ化合物粉末の重量がこの範囲よりも少ない場合は、結晶性の窒化ホウ素ナノシートの代わりに非晶質の窒化ホウ素が得られる。
In the above operation, the weight ratio of the B—N—O compound powder to the boron oxide powder in the mixture 7 is preferably in the range of 80:20 to 95: 5.
If the weight of the B—N—O compound powder is larger than this range, the target boron nitride nanosheet cannot be obtained, and nanotubes and nanoparticles are generated. When the weight of the B—N—O compound powder is less than this range, amorphous boron nitride is obtained instead of the crystalline boron nitride nanosheet.
また、混合物７全体と珪素粉末５との重量比は３：１〜１：２の範囲が好ましく、混合物７の重量がこの範囲よりも多いと、窒化ホウ素ナノシートが凝集してしまう。そして、混合物７の重量がこの範囲よりも少ない場合は窒化珪素ナノワイヤーの全面が窒化ホウ素ナノシートで完全に覆われない。
生成された、窒化珪素ナノワイヤー及びその上の窒化ホウ素ナノシートは、坩堝６の内壁に析出し、肉眼では白色のスポンジ状の物質に見える。
Further, the weight ratio of the entire mixture 7 to the silicon powder 5 is preferably in the range of 3: 1 to 1: 2, and if the weight of the mixture 7 is larger than this range, the boron nitride nanosheets aggregate. When the weight of the mixture 7 is less than this range, the entire surface of the silicon nitride nanowire is not completely covered with the boron nitride nanosheet.
The generated silicon nitride nanowire and the boron nitride nanosheet thereon are deposited on the inner wall of the crucible 6 and appear to be a white sponge-like substance with the naked eye.
上記の製造方法によれば、単結晶のα型六方晶系窒化珪素ナノワイヤーが得られ、この表面に窒化ホウ素ナノシートが成長し、窒化珪素ナノワイヤーを被覆する。この窒化ホウ素ナノシートは六方晶系窒化ホウ素ナノシートである。この窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーは、後述するように、長さが数十μｍ（マイクロメートル）で、直径が約２００ｎｍ（ナノメートル）であり、例えばカーボンナノチューブなどのナノチューブよりも長さ及び直径が大きくなるので、取り扱いが容易となる。このため、この材料を用いた冷陰極の形成が容易にできる。 According to the above manufacturing method, single crystal α-type hexagonal silicon nitride nanowires are obtained, and boron nitride nanosheets are grown on the surface to cover the silicon nitride nanowires. This boron nitride nanosheet is a hexagonal boron nitride nanosheet. As will be described later, the silicon nitride nanowire coated with the boron nitride nanosheet has a length of several tens of micrometers (micrometers) and a diameter of about 200 nm (nanometers). Since the length and diameter are increased, the handling becomes easy. For this reason, it is possible to easily form a cold cathode using this material.
次に、実施例に基づいて詳細に説明する。
初めに、Ｂ−Ｎ−Ｏ化合物粉末を次のようにして合成した。
１０００ｃｍ3 の水に０．４モル（ｍｏｌ）のホウ酸を１００℃で溶解し、この溶液に０．２モルのメラミンを徐々に添加し、添加終了後、室温に冷却して２日間放置し、白色粉末を沈殿させた。白色粉末を乾燥後、さらに脱水するため、空気中で５００℃、２時間加熱後、窒素中で８００℃、１時間加熱して、化学式Ｂ4 Ｎ3 Ｏ2 Ｈで表される黄色の化合物粉末を得た。
さらに、この黄色化合物を空気中で６００℃、２時間焼成して酸素含有量の高い白色のＢ−Ｎ−Ｏ化合物粉末を得た。
Next, it demonstrates in detail based on an Example.
First, a B—N—O compound powder was synthesized as follows.
0.4 mol (mol) of boric acid was dissolved in 1000 cm 3 of water at 100 ° C., and 0.2 mol of melamine was gradually added to this solution. After the addition was completed, the solution was cooled to room temperature and left for 2 days. A white powder was precipitated. In order to further dehydrate the white powder after drying, it is heated in air at 500 ° C. for 2 hours, then in nitrogen at 800 ° C. for 1 hour, and a yellow compound powder represented by the chemical formula B 4 N 3 O 2 H Got.
Further, this yellow compound was calcined in air at 600 ° C. for 2 hours to obtain a white B—N—O compound powder having a high oxygen content.
次に、窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーを、次のようにして合成した。
ホウ酸とメラミンから合成したＢ−Ｎ−Ｏ化合物粉末１．８ｇと和光純薬工業（株）製の酸化ホウ素粉末（純度９９％）０．２ｇと、の混合物７をグラファイト坩堝８に入れ、この坩堝８を図１に示した縦型高周波誘導加熱装置１の図示しないサセプターに取り付けた。
和光純薬工業（株）製の珪素粉末５（純度９９．９％）１ｇを窒化ホウ素坩堝６に入れ、グラファイト坩堝８の上方に配置した。縦型高周波誘導加熱装置１内に窒素ガス１０を１．５リットル／分の流量で流しながら、１５００℃で３０分間加熱した。
Next, silicon nitride nanowires coated with boron nitride nanosheets were synthesized as follows.
A mixture 7 of 1.8 g of a B—N—O compound powder synthesized from boric acid and melamine and 0.2 g of boron oxide powder (purity 99%) manufactured by Wako Pure Chemical Industries, Ltd. was placed in a graphite crucible 8. This crucible 8 was attached to a susceptor (not shown) of the vertical high frequency induction heating apparatus 1 shown in FIG.
1 g of silicon powder 5 (purity 99.9%) manufactured by Wako Pure Chemical Industries, Ltd. was placed in a boron nitride crucible 6 and placed above the graphite crucible 8. Heating was performed at 1500 ° C. for 30 minutes while flowing a nitrogen gas 10 through the vertical high-frequency induction heating apparatus 1 at a flow rate of 1.5 liters / minute.
引き続き、ガス１０として窒素ガス１．５リットル／分及びアンモニアガス０．０５リットル／分の流量で流しながら、１７５０℃で１時間加熱した。加熱終了後、アンモニアガスの供給を止め、窒素ガスだけを流しながら室温まで冷却した。窒化ホウ素坩堝６の内壁に、白色のスポンジ状物質が０．５ｇ堆積した。 Subsequently, the gas 10 was heated at 1750 ° C. for 1 hour while flowing at a flow rate of nitrogen gas of 1.5 liters / minute and ammonia gas of 0.05 liters / minute. After the heating was completed, the supply of ammonia gas was stopped, and the mixture was cooled to room temperature while flowing only nitrogen gas. On the inner wall of the boron nitride crucible 6, 0.5 g of a white sponge-like substance was deposited.
図２は、実施例で合成した堆積物の走査型電子顕微鏡像を示す図である。図２から、合成した堆積物は、長さが数十μｍ（マイクロメートル）で、直径が約２００ｎｍ（ナノメートル）であることが分かる。 FIG. 2 is a view showing a scanning electron microscope image of the deposit synthesized in the example. It can be seen from FIG. 2 that the synthesized deposit has a length of several tens of micrometers (micrometers) and a diameter of about 200 nm (nanometers).
図３は、実施例で合成した堆積物の透過型電子顕微鏡像を示す図である。図３から、ナノワイヤーの両側に、数ｎｍの非常に薄いシート状物が突き出していることが分かる。 FIG. 3 is a transmission electron microscope image of the deposit synthesized in the example. From FIG. 3, it can be seen that a very thin sheet-like material of several nm protrudes on both sides of the nanowire.
図４は、実施例で合成した堆積物のナノワイヤー部のエネルギー分散型Ｘ線分析（ＥＤＸ：Ｅｎｅｒｇｙ−Ｄｉｓｐｅｒｓｉｖｅ Ｘ−ｒａｙ Ａｎａｌｙｓｉｓ）による測定結果を示す図である。図の縦軸はＸ線強度（任意目盛り）を示し、横軸はＸ線のエネルギー（ｋｅＶ）を示している。図のＥＤＸスペクトルから、ナノワイヤーの組成は珪素と窒素からなり、その組成分析から窒化珪素であることが分かる。なお、銅のピークは試料作製のために用いた銅グリッドに由来するものである。 FIG. 4 is a diagram showing measurement results by energy-dispersive X-ray analysis (EDX) of the nanowire portion of the deposit synthesized in the example. In the figure, the vertical axis represents the X-ray intensity (arbitrary scale), and the horizontal axis represents the X-ray energy (keV). From the EDX spectrum of the figure, it can be seen that the composition of the nanowire is composed of silicon and nitrogen, and the composition analysis shows that it is silicon nitride. The copper peak is derived from the copper grid used for sample preparation.
図５は、実施例で合成した窒化珪素ナノワイヤー上の突き出している部分のシート状物の電子線エネルギー損失分光装置（ＥＥＬＳ：Ｅｌｅｃｔｒｏｎ Ｅｎｅｒｇｙ Ｌｏｓｓ Ｓｐｅｃｔｒｏｍｅｔｅｒ）による測定結果を示す図である。図の縦軸は電子エネルギー強度（任意目盛り）を示し、横軸は損失エネルギー（ｅＶ）を示している。図のＥＥＬＳスペクトルから、窒化珪素ナノワイヤー上の突き出している部分のシート状物質の組成が窒化ホウ素であることが確認された。 FIG. 5 is a diagram illustrating a measurement result of an protruding portion of the sheet-like material on the silicon nitride nanowire synthesized in the example by an electron energy loss spectrometer (EELS). The vertical axis of the figure represents the electron energy intensity (arbitrary scale), and the horizontal axis represents the loss energy (eV). From the EELS spectrum of the figure, it was confirmed that the composition of the protruding sheet-like material on the silicon nitride nanowire was boron nitride.
さらに、電子線回折測定の結果から、ナノワイヤー部分は格子定数ａ＝０．７７ｎｍ、ｃ＝０．５６ｎｍを有する単結晶のα型窒化珪素であることが分かった。また、ナノシート部分は面間距離０．３３ｎｍを有する六方晶系窒化ホウ素ナノシートであることが分かった。これにより、実施例で合成した堆積物は、α型六方晶系窒化珪素ナノワイヤーが、六方晶系窒化ホウ素ナノシートで被覆されている、即ち、窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーであることが分かった。 Furthermore, from the results of electron beam diffraction measurement, the nanowire portion was found to be single crystal α-type silicon nitride having lattice constants a = 0.77 nm and c = 0.56 nm. Further, it was found that the nanosheet portion was a hexagonal boron nitride nanosheet having an interplane distance of 0.33 nm. Accordingly, the deposit synthesized in the example is a silicon nitride nanowire in which the α-type hexagonal silicon nitride nanowire is coated with the hexagonal boron nitride nanosheet, that is, the boron nitride nanosheet coated with the boron nitride nanosheet. I understood that.
図６は、実施例で得られた窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーの電界放出による電流−電圧特性（Ｉ−Ｖ特性）の測定結果を示す図である。図において、横軸は印加電圧（Ｖ）を示し、縦軸は電流密度（ｍＡ／ｃｍ2 ）を示している。また、挿入図は、低電流密度（μＡ／ｃｍ2 ）におけるＩ−Ｖ特性を示している。ここで、窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーによる陰極と陽極との距離は、２００μｍとした。
図から明らかなように、電流密度が０．０１ｍＡ／ｃｍ2 のときの電圧から、電流が流れる開始電界強度は４．２Ｖ／μｍである。また、電流密度が１０ｍＡ／ｃｍ2 のときの電圧から、電流が流れる閾値電界強度は４．４Ｖ／μｍであることが分かった。また、１１００Ｖの印加電圧（電界強度は５．５Ｖ／μｍ）で、電流密度が７００ｍＡ／ｃｍ2 となり、大きな電流密度及び急峻なＩ−Ｖ特性が得られることが分かった。
FIG. 6 is a diagram showing measurement results of current-voltage characteristics (IV characteristics) by field emission of silicon nitride nanowires coated with boron nitride nanosheets obtained in the examples. In the figure, the horizontal axis represents the applied voltage (V), and the vertical axis represents the current density (mA / cm 2 ). Further, the inset shows the IV characteristics at a low current density (μA / cm 2 ). Here, the distance between the cathode and the anode by the silicon nitride nanowire covered with the boron nitride nanosheet was 200 μm.
As is apparent from the figure, the starting electric field strength through which the current flows is 4.2 V / μm from the voltage when the current density is 0.01 mA / cm 2 . Further, from the voltage when the current density was 10 mA / cm 2 , it was found that the threshold electric field strength through which the current flows was 4.4 V / μm. It was also found that a current density of 700 mA / cm 2 was obtained at an applied voltage of 1100 V (electric field strength of 5.5 V / μm), and a large current density and steep IV characteristics were obtained.
ここで、比較のために、窒化珪素ナノワイヤーの電界放出特性を測定した。Ｉ−Ｖ特性の測定から、開始電界強度は８Ｖ／μｍであり、印加電圧が１１００Ｖのときに約１０μＡという低電流しか得られなかった。
これにより、実施例の窒化ホウ素ナノシートで覆われた窒化珪素ナノワイヤーの電界放出における電流−電圧特性は低電界強度で、非常に急峻なＩ−Ｖ特性が得られ、この特性
はカーボンチューブによる電界放出特性（例えば、非特許文献１参照）に匹敵することが明らかとなった。
Here, for comparison, the field emission characteristics of silicon nitride nanowires were measured. From the measurement of the IV characteristics, the starting electric field strength was 8 V / μm, and when the applied voltage was 1100 V, only a low current of about 10 μA was obtained.
Thereby, the current-voltage characteristic in the field emission of the silicon nitride nanowire covered with the boron nitride nanosheet of the example is low electric field strength, and a very steep IV characteristic is obtained. It became clear that it is comparable with a release characteristic (for example, refer nonpatent literature 1).
本発明によれば、化学的安定性に優れ、かつ、ナノサイズの窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーが得られるので、例えば、この材料を冷陰極材料としたディスプレイや電子ビーム露光装置を製造することができる。 According to the present invention, a silicon nitride nanowire excellent in chemical stability and coated with a nano-sized boron nitride nanosheet can be obtained. For example, a display or electron beam exposure apparatus using this material as a cold cathode material Can be manufactured.
１：縦型高周波誘導加熱装置
２：反応管
３：誘導加熱コイル
４：誘導加熱コイル
５：珪素粉末
６：第１の坩堝
７：Ｂ−Ｎ−Ｏ化合物粉末及び酸化ホウ素粉末の混合物
８：第２の坩堝
９：Ｂ−Ｎ−Ｏ化合物蒸気
１０：窒素ガス、または、窒素ガス及びアンモニアガスの混合ガス
1: vertical high frequency induction heating device 2: reaction tube 3: induction heating coil 4: induction heating coil 5: silicon powder 6: first crucible 7: mixture of B—N—O compound powder and boron oxide powder 8: first 2 crucible 9: B—N—O compound vapor 10: nitrogen gas or a mixed gas of nitrogen gas and ammonia gas
Claims (9)
次に、窒素ガス及びアンモニアガスの混合ガス雰囲気中で、ホウ素と窒素と酸素とから成る化合物粉末と酸化ホウ素粉末との重量比が８０：２０〜９５：５の範囲の混合物を加熱することによって、上記窒化珪素ナノワイヤーを窒化ホウ素ナノシートで被覆することを特徴とする、窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーの製造方法。
By synthesizing silicon nitride nanowires by heating silicon powder in a nitrogen gas atmosphere,
Next, in a mixed gas atmosphere of nitrogen gas and ammonia gas, by heating a mixture in which the weight ratio of the compound powder composed of boron, nitrogen, and oxygen and the boron oxide powder is in the range of 80:20 to 95: 5 A method for producing silicon nitride nanowires coated with boron nitride nanosheets, wherein the silicon nitride nanowires are coated with boron nitride nanosheets.
及び酸化ホウ素粉末の混合物を入れた坩堝と、を配置し、
窒素ガスを流しながら、上記珪素を１３５０〜１５５０℃の温度範囲で加熱して窒化珪
素ナノワイヤーを合成し、
次に、窒素ガス及びアンモニアガスの混合ガス雰囲気中で、ホウ素と窒素と酸素とから成る化合物粉末と酸化ホウ素粉末との重量比が８０：２０〜９５：５の範囲の混合物を１４００〜１８００℃の温度範囲で加熱することによって、上記窒化珪素ナノワイヤーを窒化ホウ素ナノシートで被覆することを特徴と
する、窒化ホウ素ナノシートで被覆された窒化珪素ナノワイヤーの製造方法。
In each heating furnace, a crucible containing silicon powder and a crucible containing a mixture of a compound of boron, nitrogen and oxygen and boron oxide powder were disposed,
While flowing nitrogen gas, the silicon is heated in a temperature range of 1350 to 1550 ° C. to synthesize silicon nitride nanowires,
Next, in a mixed gas atmosphere of nitrogen gas and ammonia gas, a mixture in which the weight ratio of the compound powder composed of boron, nitrogen, and oxygen to the boron oxide powder is in the range of 80:20 to 95: 5 is 1400 to 1800 ° C. A method for producing silicon nitride nanowires coated with boron nitride nanosheets, wherein the silicon nitride nanowires are coated with boron nitride nanosheets by heating in a temperature range of
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| JP2004161569A (en) * | 2002-11-14 | 2004-06-10 | National Institute For Materials Science | Nanowhisker and its manufacturing process |
| JP2004210562A (en) * | 2002-12-27 | 2004-07-29 | National Institute For Materials Science | Silicon carbide nanowire or silicon nitride nanowire coated with boron nitride, and production method therefor |
| JP2004231456A (en) * | 2003-01-29 | 2004-08-19 | National Institute For Materials Science | SILICON NITRIDE (Si3N4) NANOROD AND ITS MANUFACTURING METHOD |
| JP2005075656A (en) * | 2003-08-28 | 2005-03-24 | National Institute For Materials Science | Boron nitride nanowire and method of manufacturing the same |
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