CN101224887A

CN101224887A - Preparation technology of silicon nano-tube/nano-wire

Info

Publication number: CN101224887A
Application number: CNA2008100141466A
Authority: CN
Inventors: 毕见强; 白玉俊; 亓永新; 朱慧灵; 庞林林; 王伟礼; 韩福东; 李少杰
Original assignee: Shandong University
Current assignee: Shandong University
Priority date: 2008-02-03
Filing date: 2008-02-03
Publication date: 2008-07-23
Anticipated expiration: 2028-02-03
Also published as: CN100564257C

Abstract

The invention provides a technology for preparing a silicon nanometer tube/nanometer wire, which belongs to the technical field of an inorganic non-metal material preparation method and includes the following steps: weigh silicon tetrachloride and excessive zinc powder to be poured into a reaction vessel, raise the temperature to 450-550 DEG C and keep the temperature for 8-12 hours so as to lead the reactants to react, then cool the reaction vessel and reaction products are washed by hydrochloric acid and deionized water, then filtered and dried for 3-8 hours at the temperature of 50-60 DEG C to obtain brown or grey powder, which is the silicon nanometer tube/nanometer wire. The invention adopts the silicon tetrachloride as a silicon source, zinc as a reducer and a metal solvent and prepares the silicon nanometer tube and the nanometer wire by utilizing the floating force of the liquefied zinc above the melting point of the zinc; the invention has the advantages of short reaction time, high purity of the product, high production rate, good repeatability and so on.

Description

A kind of preparation technology of nano-tube/nano wire

Technical field

The present invention relates to a kind of preparation technology of nano-tube/nano wire, belong to ceramic preparation method technical field.

Background technology

Silicon has in hyundai electronics industry extensively and important use, the silicon of nanoscale, have the good optical performance as nano wire, porous silicon etc., received increasing concern: the nano wire of silicon is widely used in accurate device and photoelectron and biological fields such as transmitter, logical gate, storer.Current research finds that the nano-array of silicon has very excellent thermoelectric property, can be used for developing cheap thermoelectric material, improves the efficient of large-scale coal fired power generation machine and micro solar battery.

At present, the preparation method of silicon nanowires has: (1) with containing small amount of Fe, Co, and the silicon source of metal catalysts such as Ni as shielding gas, is carried out laser ablation at a certain temperature and is prepared silicon nanowires with Ar gas as target; (2) with Au, Fe, metals such as Ni are equipped with silicon nanowires as catalyzer by vapour deposition (CVD) legal system; (3) direct heat evaporation solid state si source under 1200 ℃ high temperature deposits on the substrate preparation silicon nanowires then; (4) oxide compound assisting growth silicon nanowires; (5) prepare silicon nanowires with porous alumina, zeolite etc. as template; (6) prepare silicon nanowires according to supercritical solution-liquid-solid (SFLS) growth mechanism; (7) Gu prepare silicon nanowires according to solid-liquid-(SLS) growth mechanism; (8) adopt molecular beam epitaxy (MBE) legal system to be equipped with silicon nanowires.

The preparation method of nano-tube has: (1) has the Al of nanochannel ₂O ₃Deposited gold is made catalyzer in the substrate, is equipped with nano-tube by the CVD legal system; (2) on porous alumina, adopt the molecular beam epitaxial growth nano-tube; (3) be that template is carried out epitaxy with the ZnS nano wire, dissolve away the ZnS nano wire then and obtain nano-tube; (4) by the Hydrothermal Preparation nano-tube; (5) by direct current-arc plasma technology growth nano-tube; (6) silane carries out Pintsch process and prepares nano-tube under the catalytic condition of gold; (7) unite use template and CVD technology and prepare nano-tube.

Therefore, preparation silicon nanowires and nanotube method generally all need be carried out at the high temperature more than 1000 ℃ at present, and need catalyzer, equipment complexity not only, and long reaction time, product purity low (existing metal catalyst to pollute), cost height have brought inconvenience for the application of silicon nanowires and nanotube.

Summary of the invention

At above-mentioned the deficiencies in the prior art, the invention provides a kind of preparation technology of nano-tube/nano wire, step is as follows:

(1). take by weighing zinc powder, measure liquid silicon tetrachloride, wherein, the zinc powder quality is 2g: 1ml～6g: 1ml with the ratio of silicon tetrachloride volume, pack into then in the reactor, seal tight reactor, in process furnace, be heated to 450～550 ℃, and be incubated 8～12 hours, make following reaction: SiCl takes place between two kinds of reactants ₄+ 2Zn=Si+2ZnCl ₂, close process furnace then, make reactor naturally cooling in stove, be cooled to room temperature;

(2). clean cooled reaction product with hydrochloric acid, suction filtration is removed Residual reactants then;

(3). clean above-mentioned reaction product with ionized water, suction filtration is removed byproduct of reaction then;

(4). products therefrom after drying 3～8 hours under 50～60 ℃ of temperature, is got brown or grey powder, be nano-tube/nano wire.

Weighing zinc powder and measure silicon tetrachloride and in the anhydrous and oxygen-free glove box, carry out in the described step (1).

The present invention is with silicon tetrachloride (SiCl ₄) as the silicon source, as reductive agent and metal solvent, more than the fusing point (419.58 ℃) of zinc, utilize the buoyancy of liquid Zn to prepare nano-tube and nano wire with zinc; Characteristics of the present invention are: react under the buoyancy of liquid Zn and lower temperature, reaction time consumption is short, the product purity height, and the productive rate height, favorable repeatability is the method that a kind of ideal prepares nano-tube/nano wire.

Description of drawings

The x-ray diffraction pattern of the product that Fig. 1 makes for embodiment 1;

The shape appearance figure a (100nm) of the product that Fig. 2 makes for embodiment 1;

The shape appearance figure b (200nm) of the product that Fig. 3 makes for embodiment 1;

The shape appearance figure c (200nm) of the product that Fig. 4 makes for embodiment 1;

The shape appearance figure d (200nm) of the product that Fig. 5 makes for embodiment 1;

The shape appearance figure e (200nm) of the product that Fig. 6 makes for embodiment 1.

Embodiment

Embodiment 1: preparation nano-tube and silicon nanowires:

In the anhydrous and oxygen-free glove box, weigh in the balance and get 15g Zn powder, measure 4ml SiCl with transfer pipet ₄, move in the 30ml reactor, seal tight reactor, in process furnace, be heated to 550 ℃ and be incubated 10 hours, close process furnace, make reactor in stove, naturally cool to room temperature, with hydrochloric acid cleaning reaction product, suction filtration, colourless to filtrate, use deionized water cleaning reaction product again, be neutral to filtrate, then product was dried 3 hours at 50 ℃, obtain brown ceramic powder 0.9g, nanotube and nano wire in the product account for more than 80%.

As shown in Figure 1, the silicon of each diffraction peak and face-centred cubic structure is very identical among the figure, lattice parameter a=5.438 ; From Fig. 2, can observe a large amount of nano-tubes and nano wire, pattern by sample can confirm that nano-tube and nano wire are under the buoyancy of liquid Zn, liquid level direction growth perpendicular to solvent zinc forms, and the forming process of nano-tube and nano wire can be described.

Embodiment 2: preparation nano-tube and silicon nanowires:

In the anhydrous and oxygen-free glove box, weigh in the balance and get 15g Zn powder, measure 3ml SiCl with transfer pipet ₄, move in the 30ml reactor, seal tight reactor, in process furnace, be heated to 550 ℃ and be incubated 1 hour, close process furnace, make reactor in stove, naturally cool to room temperature, with hydrochloric acid cleaning reaction product, suction filtration, colourless to filtrate, use deionized water cleaning reaction product again, be neutral to filtrate, then product dried 3 hours at 50 ℃, obtain minute quantity grey powder, illustrate that soaking time is short, SiCl ₄Be difficult to abundant reaction with Zn, cause the product amount that obtains few.

Embodiment 3: preparation nano-tube and silicon nanowires:

In the anhydrous and oxygen-free glove box, weigh in the balance and get 15g Zn powder, measure 3ml SiCl with transfer pipet ₄, move in the 30ml reactor, seal tight reactor, in process furnace, be heated to 450 ℃ and be incubated 20 hours, close process furnace, make reactor in stove, naturally cool to room temperature, with hydrochloric acid cleaning reaction product, suction filtration, colourless to filtrate, use deionized water cleaning reaction product again, be neutral to filtrate, then product was dried 3 hours at 50 ℃, obtain brown ceramic powder 0.6g, nanotube and nano wire in the product account for 40%.

Embodiment 4: preparation nano-tube and silicon nanowires:

In the anhydrous and oxygen-free glove box, weigh in the balance and get 15g Zn powder, measure 2ml SiCl with transfer pipet ₄Move in the 30ml reactor, seal tight reactor, in process furnace, be heated to 600 ℃ and be incubated 20 hours, close process furnace, make reactor in stove, naturally cool to room temperature, with hydrochloric acid cleaning reaction product, suction filtration, colourless to filtrate, use deionized water cleaning reaction product again, be neutral to filtrate, then product dried 3 hours at 50 ℃, obtain grey powder 0.4g, the product form is mainly nanoparticle, have minor amount of silicon nanotube and nano wire, and the amount of nano wire illustrates the too high formation that is unfavorable for nano-tube and nano wire of temperature more than the amount of nanotube, may be since temperature too high, the atom of silicon be gathered into particle's velocity person greater than nano-tube and nano wire the speed of growth under buoyancy.

Embodiment 5: preparation nano-tube and silicon nanowires:

In the anhydrous and oxygen-free glove box, weigh in the balance and get the 5.4g sodium Metal 99.5, measure 3ml SiCl with transfer pipet ₄Move in the 30ml reactor, seal tight reactor, in process furnace, be heated to 550 ℃ and be incubated 10 hours, close process furnace, make reactor in stove, naturally cool to room temperature, earlier with dehydrated alcohol cleaning reaction product to remove remaining sodium Metal 99.5, and then with hydrochloric acid cleaning reaction product, suction filtration, colourless to filtrate, use deionized water cleaning reaction product again, be neutral to filtrate, then product dried 3 hours at 50 ℃, obtain the 0.6g dark gray powder, there is variform in the product, based on hollow ball, only form a small amount of very short nanotube and nano wire, the buoyancy of visible liquid Zn has played keying action in the process of synthetic nano-tube and nano wire.

Claims

1. the preparation technology of a nano-tube/nano wire, it is characterized in that: step is as follows:

(1). take by weighing zinc powder, measure liquid silicon tetrachloride, wherein, the zinc powder quality is 2g: 1ml～6g: 1ml with the ratio of silicon tetrachloride volume, pack into then in the reactor, seal tight reactor, in process furnace, be heated to about 450～550 ℃, and be incubated 8～12 hours, make following reaction: SiCl takes place between two kinds of reactants ₄+ 2Zn=Si+2ZnCl ₂, close process furnace then, make reactor naturally cooling in stove, be cooled to room temperature;

2. the preparation technology of a kind of nano-tube/nano wire according to claim 1 is characterized in that: weighing zinc powder and measure silicon tetrachloride and carry out in the anhydrous and oxygen-free glove box in the described step (1).