JP4547519B2 - Method for producing silicon nanowire - Google Patents
Method for producing silicon nanowire Download PDFInfo
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- JP4547519B2 JP4547519B2 JP2004307618A JP2004307618A JP4547519B2 JP 4547519 B2 JP4547519 B2 JP 4547519B2 JP 2004307618 A JP2004307618 A JP 2004307618A JP 2004307618 A JP2004307618 A JP 2004307618A JP 4547519 B2 JP4547519 B2 JP 4547519B2
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Description
本願発明は、シリコンナノワイヤーの製造方法に関するものである。 The present invention relates to a method for producing silicon nanowires.
シリコンナノワイヤーの応用として、マイクロマシン用の素材、ナノサイズの半導体が考えられる。特に、半導体への応用では、リソグラフィー技術のように、回路に直接シリコンナノワイヤーが組み込まれるのが望ましい。そのためには、回路に損傷を与えないように、できるだけ低温でシリコンナノワイヤーが合成される必要がある。 Silicon nanowires can be applied to materials for micromachines and nano-sized semiconductors. In particular, in semiconductor applications, it is desirable to incorporate silicon nanowires directly into the circuit as in lithography technology. For this purpose, it is necessary to synthesize silicon nanowires at the lowest possible temperature so as not to damage the circuit.
従来、シリコンナノワイヤーの製造は、シリコンの溶融蒸発を利用した方法で行われているが、この方法では、基板温度は1000℃近い高温が必要とされる。これに対し、シランガスの熱分解を利用する気相化学反応を用い、さらに、Ａｕ、Ｆｅ、Ｎｉ粒子等の触媒を利用すると、基板温度が比較的低い温度でシリコンナノワイヤーが作製される。 Conventionally, the production of silicon nanowires has been performed by a method using melt evaporation of silicon, but this method requires a substrate temperature as high as about 1000 ° C. In contrast, when a gas phase chemical reaction utilizing thermal decomposition of silane gas is used and a catalyst such as Au, Fe, or Ni particles is used, silicon nanowires are produced at a relatively low substrate temperature.
最近、モノシラン（ＳｉＨ4）を用いて500℃でシリコンナノワイヤーの合成が行われている（たとえば、非特許文献１参照）。
しかしながら、半導体基板回路に熱損傷を与えないためには、さらに低温でのシリコンナノワイヤーの合成が望まれる。 However, in order not to cause thermal damage to the semiconductor substrate circuit, synthesis of silicon nanowires at a lower temperature is desired.
本願発明は、このような事情に鑑みてなされたものであり、300℃以下の温度で結晶性
のシリコンナノワイヤーが生成するシリコンナノワイヤーの製造方法を提供することを解決すべき課題としている。
This invention is made | formed in view of such a situation, and makes it the subject which should be solved to provide the manufacturing method of the silicon nanowire which a crystalline silicon nanowire produces | generates at the temperature of 300 degrees C or less.
本願発明は、上記の課題を解決するために、第１には、シリコンと低融点の共晶合金を作る金属を触媒としてポリシランガスの熱分解によりシリコンナノワイヤーを生成させることを特徴としている。 In order to solve the above problems, the present invention is characterized in that, first, silicon nanowires are generated by thermal decomposition of polysilane gas using a metal that forms a eutectic alloy having a low melting point with silicon as a catalyst.
本願発明は、第２には、触媒は、金、銀、鉄またはニッケルから選択されるいずれか１種であることを特徴としている。 Secondly, the present invention is characterized in that the catalyst is any one selected from gold, silver, iron and nickel.
本願発明は、第３には、ポリシランガスがジシランガスであることを特徴としている。 Third, the present invention is characterized in that the polysilane gas is a disilane gas.
本願発明によれば、300℃以下の温度で結晶性のシリコンナノワイヤーを合成すること
ができる。このため、半導体回路基板に熱損傷を与えずに、半導体回路に直接シリコンナノワイヤーを組み込むことが可能となる。
According to the present invention, crystalline silicon nanowires can be synthesized at a temperature of 300 ° C. or lower. For this reason, it becomes possible to incorporate silicon nanowires directly into the semiconductor circuit without causing thermal damage to the semiconductor circuit substrate.
以下、実施例を示しつつ、本願発明のシリコンナノワイヤーの製造方法についてさらに詳しく説明する。 Hereinafter, the manufacturing method of the silicon nanowire of the present invention will be described in more detail with reference to examples.
これまでに報告されているシランの生成熱、エントロピーおよび比熱データに基づいて、シリコンが生成する分解生成自由エネルギーを計算し、温度の関数として図１に示した。 Based on the heat of formation, entropy, and specific heat data of silane reported so far, the decomposition free energy generated by silicon was calculated and shown in FIG. 1 as a function of temperature.
いずれのシランガスも、分解生成自由エネルギーは室温以上では負の値をとる。一方、モノシラン（ＳｉＨ4）に比べてジシラン（Ｓｉ2Ｈ6）、トリシラン（Ｓｉ3Ｈ8）のポリ
シランの分解生成自由エネルギーは負側に倍以上大きく、室温付近でも十分に負の値をとる。このことから、ポリシランは、低温でも分解しやすいと理解され、モノシランに比べてより低温でシリコンが生成すると予測される。
In any silane gas, the decomposition free energy takes a negative value at room temperature or higher. On the other hand, polysilane decomposition free energy of disilane (Si 2 H 6 ) and trisilane (Si 3 H 8 ) is more than double on the negative side compared to monosilane (SiH 4 ), and takes a sufficiently negative value near room temperature. . From this, it is understood that polysilane is easily decomposed even at a low temperature, and it is predicted that silicon is generated at a lower temperature than monosilane.
ナノワイヤーとして成長させるためには、シリコンと低融点の共晶合金を作る金属が触媒として必要であり、そのような金属として、金、銀、鉄、ニッケル等が例示される。触媒の形態としては、表面積が大きくなるように、粒子状であることが好ましい。 In order to grow as a nanowire, a metal that forms a eutectic alloy having a low melting point with silicon is required as a catalyst. Examples of such a metal include gold, silver, iron, nickel, and the like. The form of the catalyst is preferably particulate so as to increase the surface area.
シリコン基板上に金をスパッタにより蒸着し、この基板を反応容器内に配置し、反応容器内を１×１０-6Torrの真空にした。次いで、基板を296℃まで加熱し、温度が一定とな
ったところで、反応容器内にＨ2ガスで１０％に希釈したジシラン（Ｓｉ2Ｈ6）ガスを５Torrまで導入し、この状態に５分間保持した。
Gold was deposited on the silicon substrate by sputtering, this substrate was placed in a reaction vessel, and the inside of the reaction vessel was evacuated to 1 × 10 −6 Torr. Next, the substrate was heated to 296 ° C., and when the temperature became constant, disilane (Si 2 H 6 ) gas diluted to 10% with H 2 gas was introduced into the reaction vessel up to 5 Torr, and this state was maintained for 5 minutes. Retained.
基板表面を走査型電子顕微鏡で観察すると、図２に示したように、ナノワイヤーが形成されているのが確認された。ナノワイヤーは、直径が約５０nm、長さが最長で４μｍであった。Ｘ線分析の結果、表１に示したように、ナノワイヤー本体はほぼシリコンから形成されていた。300℃以下の低温でシリコンナノワイヤーが基板上に形成されたことが確認
された。
When the surface of the substrate was observed with a scanning electron microscope, it was confirmed that nanowires were formed as shown in FIG. The nanowire had a diameter of about 50 nm and a maximum length of 4 μm. As a result of X-ray analysis, as shown in Table 1, the nanowire main body was substantially formed of silicon. It was confirmed that silicon nanowires were formed on the substrate at a low temperature of 300 ° C. or lower.
また、透過型電子顕微鏡で観察した結果、図３に示したように、シリコンナノワイヤーは、シリコンの単結晶であることが確認された。 Moreover, as a result of observing with a transmission electron microscope, as shown in FIG. 3, it was confirmed that the silicon nanowire is a single crystal of silicon.
もちろん、本願発明は、以上の実施例によって限定されるものではない。ポリシランガスの種類、反応条件等の細部については様々な態様が可能である。 Of course, the present invention is not limited to the above embodiments. Various details are possible for details such as the type of polysilane gas and reaction conditions.
以上詳しく説明したとおり、本願発明によって、300℃以下の温度で結晶性のシリコン
ナノワイヤーを合成することが可能となる。
As described above in detail, the present invention makes it possible to synthesize crystalline silicon nanowires at a temperature of 300 ° C. or lower.
Claims (3)
The method for producing silicon nanowires according to claim 1 or 2, wherein the polysilane gas is disilane gas.
Priority Applications (1)
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| JP2004307618A JP4547519B2 (en) | 2004-10-22 | 2004-10-22 | Method for producing silicon nanowire |
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| JP2004307618A JP4547519B2 (en) | 2004-10-22 | 2004-10-22 | Method for producing silicon nanowire |
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| JP2006117475A JP2006117475A (en) | 2006-05-11 |
| JP4547519B2 true JP4547519B2 (en) | 2010-09-22 |
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| JP2004307618A Expired - Fee Related JP4547519B2 (en) | 2004-10-22 | 2004-10-22 | Method for producing silicon nanowire |
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Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100799570B1 (en) * | 2006-06-15 | 2008-01-31 | 한국전자통신연구원 | Fabrication method of silicon nanotube using doughnut type catalytic metal layer |
| JP2009164104A (en) | 2007-09-06 | 2009-07-23 | Canon Inc | Electrode material for negative electrode, its manufacturing method, electrode structure using the same material, and electricity storage device |
| CN101550531B (en) * | 2008-04-03 | 2013-04-24 | 清华大学 | Method for preparing silicon nano structures |
| TWI492896B (en) * | 2008-04-18 | 2015-07-21 | Hon Hai Prec Ind Co Ltd | Method of manufacturing silicon nano-structure |
| JP4518284B2 (en) * | 2008-04-21 | 2010-08-04 | ソニー株式会社 | Method for producing polysilane-modified silicon fine wire and method for forming silicon film |
| DE102010019874A1 (en) | 2010-05-07 | 2011-11-10 | Spawnt Private S.À.R.L. | Nanowire useful in photovoltaics and electronics, comprises semiconductor materials and precursors of compounds or mixtures of compounds with a direct silicon-silicon-, germanium-silicon- and/or germanium-germanium-bond |
| DE102010019565A1 (en) | 2010-05-05 | 2011-11-10 | Spawnt Private S.À.R.L. | Nanowires of novel precursors and process for their preparation |
| JP2013527831A (en) * | 2010-05-05 | 2013-07-04 | シュパウント プライベート ソシエテ ア レスポンサビリテ リミテ | Nanowires produced from novel precursors and methods for producing the same |
| JP5499406B2 (en) * | 2010-08-20 | 2014-05-21 | 国立大学法人京都大学 | Method for producing silicon nanowire |
| WO2013120011A1 (en) | 2012-02-09 | 2013-08-15 | Energ2 Technologies, Inc. | Preparation of polymeric resins and carbon materials |
| CN105190948B (en) | 2013-03-14 | 2019-04-26 | 14族科技公司 | The complex carbon material of electrochemical modification agent comprising lithium alloyage |
| US10195583B2 (en) | 2013-11-05 | 2019-02-05 | Group 14 Technologies, Inc. | Carbon-based compositions with highly efficient volumetric gas sorption |
| CN107074994B (en) | 2014-03-14 | 2021-12-14 | 14集团技术公司 | Novel method for solvent-free sol-gel polymerization and production of adjustable carbon structures therefrom |
| US20190097222A1 (en) | 2015-08-14 | 2019-03-28 | Energ2 Technologies, Inc. | Composites of porous nano-featured silicon materials and carbon materials |
| JP7115976B2 (en) | 2015-08-28 | 2022-08-09 | グループ１４・テクノロジーズ・インコーポレイテッド | Novel materials with very durable intercalation of lithium and methods for their production |
| JP7376360B2 (en) * | 2017-03-09 | 2023-11-08 | グループ１４・テクノロジーズ・インコーポレイテッド | Degradation of silicon-containing precursors on porous scaffold materials |
| US11174167B1 (en) | 2020-08-18 | 2021-11-16 | Group14 Technologies, Inc. | Silicon carbon composites comprising ultra low Z |
| US11335903B2 (en) | 2020-08-18 | 2022-05-17 | Group14 Technologies, Inc. | Highly efficient manufacturing of silicon-carbon composites materials comprising ultra low z |
| US11639292B2 (en) | 2020-08-18 | 2023-05-02 | Group14 Technologies, Inc. | Particulate composite materials |
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Patent Citations (6)
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