CN101704500B - Super-long core-shell structure silicon nanowire and preparation method thereof - Google Patents
Super-long core-shell structure silicon nanowire and preparation method thereof Download PDFInfo
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- CN101704500B CN101704500B CN 200910199052 CN200910199052A CN101704500B CN 101704500 B CN101704500 B CN 101704500B CN 200910199052 CN200910199052 CN 200910199052 CN 200910199052 A CN200910199052 A CN 200910199052A CN 101704500 B CN101704500 B CN 101704500B
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Abstract
The invention belongs to the technical field of nanomaterials, in particular to a super-long core-shell structure silicon nanowire and a preparation method thereof. The silicon nanowire is characterized by small diameter, long length, good crystalline property, thick silica shell layer and the like, wherein the diameter of the nanowire is about 5nm, and the length can be up to tens of micrometers to hundreds of micrometers. The growth direction of the silicon nanowire is (111) direction. The thickness of a silica shell layer surrounded on the periphery of the silicon nanowire is about 25nm. The thick silica shell layer can improve the mechanical strength of the silicon nanowire, enhance the anti-oxidation capacity of the silicon nanowire and keep the physical properties of the nanowire stable. The super-long silicon nanowire can lead the nanomaterial to be applied more extensively and more conveniently.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of silicon nanowires and preparation method thereof.
Background technology
Silicon nanowires is one of development in recent years silicon-based nano material focus.The silicon-based nano material has the unexistent new physical property of many general silicon materials.For example experiment shows that the energy gap of silicon nanowires is relevant with the diameter of material.When the diameter of nano wire when 7nm is reduced to 1.3nm, its energy gap will be increased to 3.5eV from 1.1eV.Therefore the different silicon nanowires of diameter will have different physical characteristics, thereby bring new application to silicon nanowires.Experiment shows that also nano wire has great luminescence generated by light effect.More than these characteristics the application in microelectronic component and opto-electronic device has brought wide prospect to silicon nanowires.
Core-shell structure silicon nanowire is a kind of silicon nanowires with the protection of Si oxide shell.The nano wire of this structure has increased the mechanical strength of silicon nanowires, and makes silicon nanowires avoid oxidation, can not change in time to keep the silicon nanowires diameter, thereby make the physical property of material keep stable.Therefore the silicon nanowires of this core-shell structure has important application prospect.
The method of grow silicon nanowires commonly used has the Fabricated by Oxide-assisted Growth Mechanism method, gas-liquid phase-solid state growth method, metallic catalyst growth method and lf growth method etc.Fabricated by Oxide-assisted Growth Mechanism method and the lf growth method silicon nanowires of core shell structure that is commonly used to grow wherein.The thickness of its silica shell of nano wire of the method growth is less than or equal to the diameter of silicon core.It is a kind of simpler that solid phase-liquid phase-solid state growth method is compared said method, efficient, the method for Fast Growth nano wire, but in report in the past, the method has been had to silica white nano-wire.And the present invention waits until that with solid phase-liquid phase-solid state growth method a kind of length reaches core shell structure silicon nanowires tens of and even hundreds of microns, and shell thickness is up to tens nanometer, and diameter only is about 5 nanometers.The inventor there is not yet similar report.
Summary of the invention
The object of the present invention is to provide a kind of length long, diameter is little, core-shell structure silicon nanowire that outsourcing silica shell is thick and preparation method thereof.
It is that the Fe film of 0.8-1.2nm is made catalyst that the present invention adopts vacuum evaporation technology deposit a layer thickness on silicon substrate.Annealed, utilize the technology of solid phase reaction, grow silicon nanowires.The silicon nanowires of growth in this way, the characteristics such as it is long to have length, and diameter is little, and the silica shell is thick.The silicon nanowires diameter of its inner core is between 5-5.5nm, and length can reach tens of microns to hundreds of microns, and general length can be 50 microns～800 microns.The silica shell thickness that is surrounded on the silicon nanowires periphery is between the 22-28nm.Abundant silica shell will improve the mechanical strength of silicon nanowires, strengthens the oxidation resistance of silicon nanowires, makes the physical property of silicon nanowires keep stable.The preparation method of this silicon nanowires is simple and easy effectively, has practicality.
The concrete making step of core-shell structure silicon nanowire of the present invention is as follows:
(1) cleans substrate.
Selecting resistivity is that P type Si (100) single-chip of 5-10 Ω cm is substrate.Substrate slice needs to do cleaning treatment before grow silicon nanowires.
(2) on silicon substrate deposit Fe film as catalyst.
Silicon substrate film after the cleaning is put into the ultrahigh vacuum molecular beam epitaxy system, in vacuum chamber, heating evaporation Fe source, deposit a layer thickness is 0.8-1.2nm Fe film on silicon chip surface.Be deposited on the Fe film system of silicon chip surface as the usefulness of the catalyst of grow silicon nanowires.
(3) grow silicon nanowires:
The silicon substrate film that is deposited with the Fe film is taken out from vacuum chamber, move into the tubular annealing stove and anneal.Pass into nitrogen and hydrogen during annealing in the pipe and mix the protective gas that forms.Total gas flow rate is controlled at 150-170L/h.Annealing temperature is 1100-1120 ℃, and annealing time is 30-35 minute.Annealing naturally cools to room temperature after finishing in annealing furnace.Silicon chip surface after the annealing forms the film of one deck grey, and silicon nanowires is namely in film.
Adopt the prepared silicon nanowires of this method, its length is 50 microns～800 microns.Nano wire is core-shell structure.Middle nuclear core is silicon nanowires, and diameter is between 5-5.5nm.The shell of parcel silicon nanowires is amorphous silica, and thickness is about between 22-28nm.The direction of growth of the silicon nanowires of nuclear core is [111] direction.
The core shell structure silicon nanowires of the present invention's preparation, abundant silica shell will improve the mechanical strength of silicon nanowires, strengthens the oxidation resistance of silicon nanowires, makes the physical property of silicon nanowires keep stable.The silicon nanowires of overlength will make this nano material obtain more extensive more easily application.
Description of drawings
Fig. 1 is the electron scanning micrograph of core shell structure silicon nanowires.
Fig. 2 is in order to the structural diagrams of the annealing furnace of grow silicon nanowires among the present invention.
Number in the figure: 1 introduces the pipeline of protective gas, 2 gas flowmeters, 3 annealing furnace pipe closes, 4 annealing furnace heaters, 5 samples (silicon chip), 6 annealing furnace heat-insulation layers.
The specific embodiment
The operating procedure of preparation silicon nanowires of the present invention is as follows:
(1) cleans substrate.
Selecting resistivity is that P type Si (100) single-chip of 5-10 Ω cm is substrate.Substrate slice needs to do cleaning treatment before grow silicon nanowires.Cleaning procedure is as follows:
I) with silicon substrate film in acetone and methyl alcohol successively each ultrasonic 5-6 minute, again at deionized water for ultrasonic 5-6 minute, to remove the organic matter that stains at substrate surface.
Ii) in sulfuric acid and hydrogen peroxide solution, soak after 15-16 minute, use deionized water rinsing 5-6 minute.The volume ratio of sulfuric acid and hydrogen peroxide can be 1: 4～and 1: 6.
Iii) put into ammoniacal liquor, hydrogen peroxide, aqueous solution immersion after 15-16 minute, use deionized water rinsing 5-6 minute.Ammoniacal liquor, hydrogen peroxide, water three's volume ratio can be 1: 1: (4～6).
Iv) in 5% hydrofluoric acid, soak the oxide layer of removing the surface in 2-3 minute.Rinse well subsequently rear for subsequent use with deionized water.
(2) on silicon substrate deposit Fe film as catalyst.
Silicon substrate film after the cleaning is put into rapidly the ultrahigh vacuum molecular beam epitaxy system.Indoor at ultrahigh vacuum, heating evaporation Fe source (purity in Fe source is 99.95%), deposit a layer thickness is 0.8-1.2nm Fe film on silicon chip surface.Vacuum during deposit Fe film in the vacuum chamber must remain on 3 * 10
-9Below the Torr.The underlayer temperature of silicon chip is room temperature, and deposition rate is 0.001～0.003nm/s.
(3) grow silicon nanowires:
The silicon substrate film that is deposited with the Fe film is taken out in MBE chamber, anneal in the quartz ampoule of immigration tubular annealing stove.Annealing furnace structure as shown in Figure 3.Pass in the pipe during annealing by highly purified nitrogen and the mixed protective gas that forms of hydrogen.Wherein the volume ratio of nitrogen and hydrogen is 19: 1～18: 2.The flow of gaseous mixture is regulated by flow controller, and total gas flow rate is controlled at 150-170L/h.Annealing temperature is 1100-1120 ℃, and annealing time is 30-35 minute.After annealing finished, sample naturally cooled to room temperature in annealing furnace.Silicon chip surface after the annealing forms the film of one deck grey, and silicon nanowires is namely in film.
Adopt the prepared silicon nanowires of this method, its length is tens not wait to the hundreds of micron.Nano wire is core-shell structure.Middle nuclear core is silicon nanowires, and diameter is about 5nm.The shell of parcel silicon nanowires is amorphous Si oxide, and thickness is about about 25nm.The direction of growth of the silicon nanowires of nuclear core is [111] direction.
Claims (3)
1. the preparation method of a super-long core-shell structure silicon nanowire is characterized in that concrete steps are as follows:
(1) cleans substrate
Selecting resistivity is 5-10 Ω cm, and P type Si (100) single-chip is substrate, before the grow silicon nanowires, first silicon substrate is cleaned;
(2) deposit Fe film
Silicon substrate film after the cleaning is put into the ultrahigh vacuum molecular beam epitaxy system, and heating evaporation Fe source in vacuum chamber is the Fe film of 0.8-1.2nm in silicon chip surface deposit a layer thickness, as the catalyst of grow silicon nanowires;
(3) grow silicon nanowires
The silicon substrate that is deposited with the Fe film is taken out from vacuum chamber, move into the tubular annealing stove and anneal, pass in the pipe during annealing by nitrogen and the mixed protective gas that forms of hydrogen, total gas flow rate is controlled at 150-170L/h, annealing temperature 1100-1120 ℃, annealing time is 30-35 minute; Annealing naturally cools to room temperature after finishing in annealing furnace, namely obtain the silicon nanowires of super-long core-shell structure, and the core in the middle of it is silicon nanowires, and diameter is 5～5.5nm, and the direction of growth of silicon nanowires is [111] direction, and length is 50 microns～800 microns; Shell is the amorphous state silica, and thickness is 22～28nm.
2. the preparation method of super-long core-shell structure silicon nanowire according to claim 1, it is characterized in that: on silicon substrate during evaporation Fe film, the vacuum of vacuum chamber is below 3 * 10-9Torr, and underlayer temperature is room temperature, and deposition rate is 0.001～0.003nm/s.
3. the preparation method of super-long core-shell structure silicon nanowire according to claim 1, it is characterized in that: the volume ratio of nitrogen and hydrogen is 19: 1～18: 2 in the protective gas of using during grow silicon nanowires.
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Non-Patent Citations (6)
| Title |
|---|
| A Laser Ablation Method for the Synthesis of Crystalline Semiconductor Nanowires;Alfredo M. Morales et al.;《SCIENCE》;19980109;第279卷;第S365-S370页 * |
| Alfredo M. Morales et al..A Laser Ablation Method for the Synthesis of Crystalline Semiconductor Nanowires.《SCIENCE》.1998,第279卷第208-211页. |
| Boon K. Teo et al..Silicon-Silica Nanowires, Nanotubes, and Biaxial Nanowires: Inside, Outside, and Side-by-Side Growth of Silicon versus Silica on Zeolite.《Inorganic chemistry》.2003,第42卷第6723-6728页. |
| Byoung Tae Park et al..Controlled growth of core–shell Si–SiOx and amorphous SiO2 nanowires directly from NiO/Si.《NANOTECHNOLOGY》.2004,第15卷第S365-S370页. |
| Controlled growth of core–shell Si–SiOx and amorphous SiO2 nanowires directly from NiO/Si;Byoung Tae Park et al.;《NANOTECHNOLOGY》;20040408;第15卷;第208-211页 * |
| Silicon-Silica Nanowires, Nanotubes, and Biaxial Nanowires: Inside, Outside, and Side-by-Side Growth of Silicon versus Silica on Zeolite;Boon K. Teo et al.;《Inorganic chemistry》;20030415;第42卷;第6723-6728页 * |
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