CN103787335B - A kind of preparation method of needlepoint type silicon nanowires - Google Patents
A kind of preparation method of needlepoint type silicon nanowires Download PDFInfo
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- CN103787335B CN103787335B CN201410023476.7A CN201410023476A CN103787335B CN 103787335 B CN103787335 B CN 103787335B CN 201410023476 A CN201410023476 A CN 201410023476A CN 103787335 B CN103787335 B CN 103787335B
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Abstract
The invention provides a kind of preparation method of needlepoint type silicon nanowires, at the Au film that the deposited on substrates 5-10nm cleaned up is thick; By the substrate-transfer of deposition Au film in PECVD reaction cavity, in 30min, be warming up to 800 DEG C of annealing 40min; Pass into the silane of 40sccm, maintain reaction pressure 32pa and build-up of luminance reaction; Then at 600-800 DEG C of sustained reaction 1h, silicon au-alloy drop can be formed after the Au film annealing of substrate sputtering sedimentation, and as the catalyzer of needlepoint type nanowire growth, after the silicon source in gas phase reaches capacity in alloy liquid droplet, silicon nanowires can separate out growth gradually, because in alloy liquid droplet, the diffusion of gold can cause its volume to reduce gradually, therefore, the nanowire diameter of catalytic growth reduces along its length and becomes tip-like, process of the present invention is simple, be convenient to large area deposition, prepared needlepoint type silicon nanowires can be widely used in the fields such as SERS.
Description
Technical field
The present invention relates to a kind of preparation method of needlepoint type silicon nanowires.
Background technology
The people such as Fleishmann in 1974 find that when studying the Raman spectrum of the Pyridine Molecules that silver electrode is adsorbed its spectral line intensity has and obviously to strengthen and by its called after surface enhanced Raman scattering (SurfaceEnhancedRamanScattering).Surface enhanced Raman scattering (SERS) is a kind of highly sensitive, high-resolution analytical technology, has had been a great concern since self-discovery.And the key of SERS research is both to have required the preparation of the substrate of excellent performance to have higher enhancement factor, and must have again good homogeneity and repeatability, simultaneously with low cost.Utilize the premium properties of one dimension semiconductor nano wire, such as good workability and larger specific surface area, the gold and silver particle producing Raman enhanced activity can be modified its surface easily, thus become the higher SERS substrate of enhancement factor, this preparation method that will be a kind of great exploitation potential for its.
Tip-like nano wire probe is as the combination of SERS technology and nanotechnology, achieve application and research widely at physics, chemistry, medicine, sensing and biological field, can be applied to and manufacture multiple nano-sensor, especially at biological field, nanoscale SERS probe by the material that is extremely widely used in identification of cell as DNA or the harm composition that is applied in detection food safety, the advantage on its needle point yardstick be traditional material incomparable.The stability of tip-like silicon nanowires, larger specific surface area, and be convenient to modify gold and silver particle, make it be widely used in every field as a kind of good SERS base material.
The method preparing silicon nanowires is at present a lot, such as laser ablation method, molecular beam epitaxy, liquid chemical method, template and chemical Vapor deposition process etc.Although these methods can control grown nano thread structure and pattern, the general bad adaptability of method, can not large-scale industrial production, and operability is not strong.Meanwhile, the nano wire prepared by aforesaid method is mostly disorderly and unsystematic, is mutually wound around.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of needlepoint type silicon nanowires.
For achieving the above object, present invention employs following technical scheme.
A preparation method for needlepoint type silicon nanowires, comprises the following steps:
Using silane as precursors, adopt plasma reinforced chemical vapour deposition (PECVD) to prepare needlepoint type silicon nanowires under the alloy liquid droplet catalysis on substrate, described alloy liquid droplet is made up of silicon and metal catalyst.
Described substrate is silicon substrate, and silicon substrate is selected from Si(100), Si(111), SiO
2silicon chip (Si/SiO
2, the thickness of zone of oxidation is 300nm) or silica glass.
Described metal catalyst is gold (Au), copper (Cu) or nickel (Ni).
The preparation method of described needlepoint type silicon nanowires specifically comprises the following steps: on the silicon substrate cleaned up, deposit Au film, the silicon substrate depositing Au film is transferred in plasma reinforced chemical vapour deposition reaction chamber and anneals, Au film forms gold-silicon alloy drop after annealing, then in described reaction chamber, pass into the silane through diluted in hydrogen of 10-100sccm, and under described reaction cavity temperature is 600-800 DEG C and radio frequency power is the condition of 15-60W sustained reaction 1h, room temperature is cooled to the furnace after reaction, silicon substrate can obtain needlepoint type silicon nanowires.
Described Au(gold) thickness of film is 5-10nm, the deposition method of described Au film is ion sputtering, and ion sputtering utilizes air for build-up of luminance gas, and sputter temperature is room temperature, and sputtering current is set to 10mA, and sputtering time is 15-90s.
The condition of described annealing is: control background vacuum in described reaction chamber and be less than or equal to 4 × 10
-4pa, is then incubated (in 800 DEG C) 40min from room temperature to 800 DEG C in 30min.
Described needlepoint type silicon nanowires is with gas-liquid-solid (VLS) pattern growth.
Described in the silane of diluted in hydrogen the volume fraction of silane be 10%.
Described needlepoint type silicon nanowires is tip-like, and the length of needlepoint type silicon nanowires is 1-3 μm, and the diameter of needlepoint type silicon nanowires is 50-100nm, and the tip of needlepoint type silicon nanowires is containing the Au particle with SERS activity.
The preparation method of described needlepoint type silicon nanowires specifically comprises the following steps:
1) first Si (100) substrate is cleaned up, utilize ion sputtering instrument at the thick Au film of the Si cleaned up (100) deposited on substrates 5-10nm;
2) by depositing Si (100) substrate-transfer of Au film in plasma reinforced chemical vapour deposition reaction chamber, controlling background vacuum in described reaction chamber and being less than or equal to 4 × 10
-4pa, is then incubated (in 800 DEG C) 40min from room temperature to 800 DEG C in 30min;
3) through step 2) after, pass into the silane through diluted in hydrogen of 40sccm to described reaction chamber, and 800 DEG C, radio frequency power controls sustained reaction 1h under 30W, cools to room temperature with the furnace after reaction.
Beneficial effect of the present invention is embodied in:
In the preparation method of needlepoint type silicon nanowires of the present invention, temperature of reaction is reduced by the effect of plasma enhancing, promote the quick growth of nano wire, due to the diffusion consumption of alloy liquid droplet, form tip-like silicon nanowires the most at last, the present invention have nanowire growth speed fast, be convenient to big area suitability for industrialized production, method feature reliable and simple to operate, the needlepoint type silicon nanowires density simultaneously prepared is very high.
By carrying out anneal to the golden film of sputtering sedimentation on silicon substrate in the present invention, define gold-silicon alloy drop, and (adopt golden effect best as the catalyzer of needlepoint type Silicon nanowire growth, but also can adopt other known metals with catalytic activity, such as copper or nickel etc.), after the silicon source in gas phase reaches capacity in alloy liquid droplet, silicon nanowires can separate out growth gradually, because in alloy liquid droplet, the diffusion of gold can cause its volume to reduce gradually, therefore, the nanowire diameter of catalytic growth reduces along its length and becomes tip-like, adopt the silicon nanowires that can obtain a large amount of tip-like in this way fast.
The needlepoint type silicon nanowires specific surface area that the present invention adopts PECVD to deposit is large, smooth surface, has good chemical stability, can modify gold and silver particle easily and as good SERS substrate.
The length of needlepoint type silicon nanowires prepared by the present invention is about 1-3 μm, diameter is about 50-100nm, the Au particle with SERS activity is contained on the silicon nanowires top of tip-like, the convenient particle again modifying gold and silver of its nanowire surface, have potential SERS application prospect, the pattern of tip-like can provide the antenna effect of a kind of SERS, greatly improves the detectivity of substrate to organic molecule, can recycle repeatedly, to reduce production and the application cost of SERS substrate simultaneously.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of PECVD depositing system; In Fig. 1: 1 is entrance of cooling water, 2 is cooling water outlet, and 3 is lobe pump, and 4 is mechanical pump, 5 is molecular pump, 6 is the silane (silane volume fraction is 10%) of diluted in hydrogen, and 7 is plasma reinforced chemical vapour deposition reaction chamber, and G1 is slide valve, V4 is blow-off valve, V3 is intake valve, and V2 is hand stop valve, and V1 is front step valve.
Fig. 2 utilizes silane to prepare the principle schematic of needlepoint type silicon nanowires as reactant gases; In Fig. 2: (a) silicon substrate deposits Au film, after (b) annealing, form alloy liquid droplet catalyzer, (c) VLS grow silicon nanowires, the needlepoint type silicon nanowires formed after (d) catalyst consumption.
Fig. 3 is for utilizing gold as catalyzer, and the alloy liquid droplet SEM after 800 DEG C of annealing schemes.
Fig. 4 a is the SEM figure of the needlepoint type silicon nanowires of preparation.
Fig. 4 b is the SEM partial enlarged drawing of the needlepoint type silicon nanowires of preparation.
Fig. 5 is the TEM figure of the needlepoint type silicon nanowires of preparation.
Fig. 6 is that result figure is swept in the power spectrum face of the needlepoint type silicon nanowires of preparation; In Fig. 6: (a) is ultimate analysis selected areas, (b) is element silicon distribution plan, and (c) is gold element distribution plan.
Fig. 7 be preparation needlepoint type silicon nanowires and columnar nanometer line to the enhancing ability comparative result figure of rhodamine 6G different characteristics Raman peaks.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
The invention provides one and utilize plasma enhanced chemical vapor deposition (PECVD) technology, prepared the method for tip-like silicon nanowires by silane as precursors.
The present invention adopts the gas-liquid-solid mechanism of the most applicable grow nanowire, is strengthened reduce temperature of reaction by plasma, improves nanowire growth speed.By ion sputtering process at substrate deposition Au film, utilize the consumption of the rear alloy liquid droplet of annealing and dimensional change to control the pattern of tip-like nano wire, the method reliability is strong, is convenient to suitability for industrialized production, effectively can controls the growth of silicon nanowires needle point.
See Fig. 2, in the present invention, on silicon substrate, the Au film of sputtering sedimentation can form gold-silicon alloy drop after annealing, and as the catalyzer of tip-like Silicon nanowire growth, after the silicon source in gas phase reaches capacity in alloy liquid droplet, silicon nanowires can separate out growth gradually, because in alloy liquid droplet, the diffusion of gold can cause its volume to reduce gradually, therefore, the nanowire diameter of catalytic growth reduces along its length and becomes tip-like, and this tip-like silicon nanowires can be widely used in the fields such as electron device, medical treatment, environment, sensing and SERS.
Specific embodiment of the present invention is:
1) cleaning: by N-type Si(100) to immerse massfraction be in the HF aqueous solution of 5% 20 seconds to substrate, put into deionized water after taking-up and soak 5 minutes, then take out, and dry up with high pure nitrogen, put into rapidly ion sputtering chamber afterwards;
2) then, at N-type Si(100) Au film that deposited on substrates one deck 5-10nm is thick, wherein, utilize air for build-up of luminance source of the gas in ion-sputtering system, after background air pressure reaches below 5-10Pa, regulate charge flow rate by the skill of handling needles, room temperature sputtering (about 20 DEG C), sputtering current maintains 10mA, and sputtering time is 30s;
3) will the N-type Si(100 of deposition Au film) substrate proceeds in plasma reinforced chemical vapour deposition (PECVD) reaction cavity and makes anneal, and the condition of annealing is: background vacuum is 4 × 10
-4pa, from room temperature to 800 DEG C in 30min, and is incubated 40min, forms active catalyzer gold-silicon alloy drop by 800 DEG C of annealing; As shown in Figure 3, after 800 DEG C of 40min annealing, substrate surface is clear there is alloy liquid droplet catalyzer;
4) after annealing, pass into the silane through diluted in hydrogen (volume fraction of silane is 10%) of 40sccm, maintain reaction pressure 32Pa, radio frequency power is build-up of luminance reaction under the condition of 30w, and the growth of silicon nanowires is carried out in temperature of reaction 800 DEG C of sustained reactions, reaction times is 1h, cools to room temperature with the furnace after reaction.As shown in Fig. 4 a, Fig. 4 b, through 800 DEG C of reactions 1h, Si(100) substrate surface can grow a large amount of needlepoint type silicon nanowires.As shown in Figure 5, prepared needlepoint type silicon nanowires is tip-like, needle point top lingering section is the gold grain not having completely consumed, can find out that prepared tip-like nano wire is silicon nanowires really from TEM photo ultimate analysis power spectrum (Fig. 6) of needlepoint type silicon nanowires, the top of tip-like silicon nanowires is the gold grain with SERS activity.
The present invention can prepare large-area, dense tip-like silicon nanowires (Fig. 4 a), in the application of surface enhanced Raman spectroscopy with it for template, the gold and silver particle with SERS activity can be modified at tip-like surface of silicon nanowires by Galvanic replacement(metathesis)reaction or magnetron sputtering.Detected by Raman spectrum, the nanowire base of this tip-like has good enhanced activity, and compared with cylindrical nano wire, the nano wire of tip-like can improve 10-20 doubly (Fig. 7) to the reinforced effects of rhodamine 6G.
Tip-like silicon nanowires prepared by the present invention can be applicable to manufacture multiple nano-sensor, nano-probe, photoelectric device, solar cell, especially SERS field detection trace analyte can reach the Single Molecule Detection limit, the advantage on its needle point yardstick and higher detectivity be traditional material incomparable.
Claims (8)
1. a preparation method for needlepoint type silicon nanowires, is characterized in that: comprise the following steps:
Using silane as precursors, adopt plasma reinforced chemical vapour deposition to prepare needlepoint type silicon nanowires under the alloy liquid droplet catalysis on substrate, described alloy liquid droplet is made up of silicon and metal catalyst;
The preparation method of described needlepoint type silicon nanowires specifically comprises the following steps: on the silicon substrate cleaned up, deposit Au film, the silicon substrate depositing Au film is transferred in plasma reinforced chemical vapour deposition reaction chamber and anneals, Au film forms gold-silicon alloy drop after annealing, then in described reaction chamber, pass into the silane through diluted in hydrogen of 10-100sccm, and under described reaction cavity temperature is 600-800 DEG C and radio frequency power is the condition of 15-60W sustained reaction 1h, room temperature is cooled to the furnace after reaction, silicon substrate can obtain needlepoint type silicon nanowires.
2. the preparation method of a kind of needlepoint type silicon nanowires according to claim 1, it is characterized in that: described substrate is silicon substrate, silicon substrate is selected from Si (100), Si (111), SiO
2silicon chip or silica glass.
3. the preparation method of a kind of needlepoint type silicon nanowires according to claim 1, it is characterized in that: the thickness of described Au film is 5-10nm, the deposition method of described Au film is ion sputtering, ion sputtering utilizes air for build-up of luminance gas, sputter temperature is room temperature, sputtering current is set to 10mA, and sputtering time is 15-90s.
4. the preparation method of a kind of needlepoint type silicon nanowires according to claim 1, is characterized in that: the condition of described annealing is: control background vacuum in described reaction chamber and be less than or equal to 4 × 10
-4pa, is then incubated 40min from room temperature to 800 DEG C in 30min.
5. the preparation method of a kind of needlepoint type silicon nanowires according to claim 1, is characterized in that: described needlepoint type silicon nanowires is with gas-liquid-solid pattern growth.
6. the preparation method of a kind of needlepoint type silicon nanowires according to claim 1, is characterized in that: described in the silane of diluted in hydrogen the volume fraction of silane be 10%.
7. the preparation method of a kind of needlepoint type silicon nanowires according to claim 1, it is characterized in that: described needlepoint type silicon nanowires is tip-like, the length of needlepoint type silicon nanowires is 1-3 μm, and the diameter of needlepoint type silicon nanowires is 50-100nm, and Au particle is contained at the tip of needlepoint type silicon nanowires.
8. the preparation method of a kind of needlepoint type silicon nanowires according to claim 1, is characterized in that: the preparation method of described needlepoint type silicon nanowires specifically comprises the following steps:
1) first Si (100) substrate is cleaned up, utilize ion sputtering instrument at the thick Au film of the Si cleaned up (100) deposited on substrates 5-10nm;
2) by depositing Si (100) substrate-transfer of Au film in plasma reinforced chemical vapour deposition reaction chamber, controlling background vacuum in described reaction chamber and being less than or equal to 4 × 10
-4pa, is then incubated 40min from room temperature to 800 DEG C in 30min;
3) through step 2) after, pass into the silane through diluted in hydrogen of 40sccm to described reaction chamber, and 800 DEG C, radio frequency power controls sustained reaction 1h under 30W, cools to room temperature with the furnace after reaction.
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| CN1796267A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院半导体研究所 | Method for preparing silicon nano line |
| CN101891145A (en) * | 2009-05-22 | 2010-11-24 | 熊长宏 | Silicon nanowire preparation by gas-liquid-solid phase method |
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| CN1796267A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院半导体研究所 | Method for preparing silicon nano line |
| CN101891145A (en) * | 2009-05-22 | 2010-11-24 | 熊长宏 | Silicon nanowire preparation by gas-liquid-solid phase method |
Non-Patent Citations (1)
| Title |
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| 硅纳米线的PECVD生长研究;徐泓等;《大学物理实验》;20100430;第23卷(第2期);第27-30页 * |
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Effective date of registration: 20180511 Address after: 710000 Huxian Fengzhen Industrial Park, Xi'an, Shaanxi Patentee after: New Mstar Technology Ltd in esdart, Xi'an Address before: No. 28 Xianning West Road, Xianning stele area, Xi'an, Shaanxi Patentee before: Xi'an Jiaotong University |