CN108483448A - A kind of porous silicon preparation method - Google Patents
A kind of porous silicon preparation method Download PDFInfo
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- CN108483448A CN108483448A CN201810635168.8A CN201810635168A CN108483448A CN 108483448 A CN108483448 A CN 108483448A CN 201810635168 A CN201810635168 A CN 201810635168A CN 108483448 A CN108483448 A CN 108483448A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
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Abstract
The invention discloses a kind of preparation methods of porous silicon, this method is stirred to react by the way that polycrystalline silica flour to be put into the mixed solution of stannous sulfate, rubble ice, ammonium hydroxide and hydrofluoric acid, product is put into ice bath stirring in the mixed solution of hydrofluoric acid, hydrogen peroxide, ammonium hydroxide, ethyl alcohol after eccentric cleaning and corrodes, boric acid is then added dropwise and nitric acid continues ice bath stirring corrosion, product carries out eccentric cleaning up to porous silicon with ultra-pure water.The preparation method of the present invention is simple, assists the porous silicon cost of etch preparation relatively low relative to silver particles, prepared porous silicon have the advantages that particle aperture it is larger, it is porous be evenly distributed, pore size it is uniform, and porous silicon surface hardly adsorbing metal particles, can be improved the using effect of porous silicon.
Description
Technical field
The present invention relates to a kind of silicon processing method, especially a kind of porous silicon preparation method.
Background technology
Porous silicon（porous Si）It is a kind of novel 1-dimention nano photon crystal material, is with nano-silicon cluster
" quantum sponge " shape micro-structure of skeleton, porous silicon is due to special surface texture and huge specific surface area, in many fields
There is utilization.Porous silicon can assist corrosion hair be made by metal, and existing metal auxiliary etch be difficult to prepare aperture compared with
Greatly, porous be evenly distributed, the porous silicon particle that pore size is similar, and to prepare porous silicon past for existing metal auxiliary etch
A large amount of metallics are adsorbed toward in porous silicon surface, influence the use of porous silicon, while prepared by existing metal auxiliary etch
The manufacturing cost of porous silicon is higher.
Therefore, smaller, porous in the presence of the porous silicon particle aperture prepared in the preparation process of porous silicon at present to be distributed not
Uniformly, pore size differs greatly and the higher disadvantage of manufacturing cost, and the easy adsorbing metal particles of porous silicon surface, influences
The using effect of porous silicon.
Invention content
The object of the present invention is to provide a kind of porous silicon preparation methods.The preparation method of the present invention is simple, relative to silver
The porous silicon cost that particle assists etch to prepare is relatively low, and larger, porous distribution is equal with particle aperture for prepared porous silicon
The use effect of porous silicon can be improved in advantage even, pore size is uniform, and porous silicon surface hardly adsorbing metal particles
Fruit.
Technical scheme of the present invention：A kind of porous silicon preparation method, includes the following steps：
(a) the polycrystalline silica flour for measuring 3-5 parts, uses hydrofluoric acid, sulfuric acid, ethyl alcohol, ultra-pure water eccentric cleaning successively；
(b) polycrystalline silica flour is put into 0.05mol/L-O.1mol/L stannous sulfates, 20-50g rubble ices, 4mol/L-6mol/L ammonia
It is stirred to react in the mixed solution of water and 4mol/L-6mol/L hydrofluoric acid 2-5 minutes, obtains A product；
(c) eccentric cleaning is carried out to A product, obtains B product；
(d) B product are put into 3-6mol/L hydrofluoric acid, 0.5%-3% hydrogen peroxide, 3mol/L-6mol/L ammonium hydroxide, 8mL-15mL ethyl alcohol
Ice bath stirring corrodes 0.5h-1.5h in mixed solution, obtains C product；
(e) 0.3mol/L-1.2mol/L boric acid is added dropwise into C product and 0.5%-1.5% nitric acid continues ice bath stirring and corrodes 0.5h-
1.5h obtains D product；
(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon.
In a kind of porous silicon preparation method above-mentioned, the particle diameter of the polycrystalline silica flour in the step (a) is 4-15 μm.
In a kind of porous silicon preparation method above-mentioned, step (b) medium floe is made of ultra-pure water.
In a kind of porous silicon preparation method above-mentioned, ice bath temperature is -10 DEG C -10 DEG C in the step (d), (e).
In a kind of porous silicon preparation method above-mentioned, the step (a), (c) and the centrifugal rotational speed of eccentric cleaning in (f) are
3000-6000 revs/min.
Compared with prior art, the present invention passes through step（b）The use of stannous sulfate is source metal, Sn ions are in the solution not
Easily crystallization, is that a large amount of Sn ionic species exist after so that Sn is assisted pore-forming, assists etch, Sn particles auxiliary rotten relative to silver particles
The porous silicon surface that erosion method is prepared is not easy to obtain purer porous silicon there are Sn crystallizations, and the using effect of porous silicon can be improved,
And it is at low cost relative to silver particles compound using tin particle compound；
The present invention passes through in step（b）The middle ice cube that ultra-pure water is added into solution and prepares, and by step（d）And step
（e）It is middle using ice bath can reduce system whole capability reduce silicon hydride generate improve porous silicon yield, and by
Step（b）And step（d）The generation of the middle hydride that silicon can be effectively reduced using ammonium hydroxide and hydrofluoric acid mixed solution is reduced
H3Si-,H2Si2-,HSi3-,H4The generation of Si is to increase the yield of porous silicon；
（b）Silicon can make the tin particle absorption in solution higher in energy under the polarization of fluorine in step（Containing defective
At surface）And crystallize, ammonia radical ion reduces hydrionic concentration in water, reduces the hydrogenation of silicon, is conducive to improve yield, uses ice cube
Reducing solution system temperature reduces Sn2+To Sn4+Transformation reduces unnecessary reaction；
（d）Due to H in step2O2/H2O is to Si/ [SiF6]-It is poor that there are oxidation-reduction potentials, constitutes primary battery, and Sn particles are
Catalyst can corrode pore-forming in the place for having Sn to adsorb.
The present invention passes through in step（d）And step（e）Substep addition low-concentration-corrosion agent can effectively prevent porous silicon by oxygen
Change and yield is more than 30%.
In conclusion the preparation method of the present invention is simple, porous silicon cost relative to silver particles auxiliary etch preparation
It is relatively low, prepared porous silicon have the advantages that particle aperture it is larger, it is porous be evenly distributed, pore size it is uniform and porous
Silicon face hardly adsorbing metal particles, can be improved the using effect of porous silicon.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) the figure A for the porous silicon that the present invention is prepared；
Fig. 2 is scanning electron microscope (SEM) the figure B for the porous silicon that the present invention is prepared.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
Embodiment 1：A kind of porous silicon preparation method, includes the following steps：
(a) the polycrystalline silica flour that 4 parts of particle diameters are 9 μm is measured, uses hydrofluoric acid, sulfuric acid, ethyl alcohol, ultra-pure water eccentric cleaning successively；
(b) by polycrystalline silica flour be put into rubble ice, 5mol/L ammonium hydroxide made of 0.08mol/L stannous sulfates, 35g ultra-pure waters and
It is stirred to react in the mixed solution of 5mol/L hydrofluoric acid 3.5 minutes, obtains A product；
(c) eccentric cleaning is carried out to A product, obtains B product；
(d) B product are put into the mixed solution of 4.5mol/L hydrofluoric acid, 2% hydrogen peroxide, 4.5mol/L ammonium hydroxide, 11.5mL ethyl alcohol,
Corrode 1h in 0 DEG C of ice bath stirring, obtains C product；
(e) 0.75mol/L boric acid is added dropwise into C product and 1% nitric acid continues to keep 0 DEG C of ice bath stirring corrosion 1h, obtains D product；
(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon；
The centrifugal rotational speed of above-mentioned steps (a), (c) and eccentric cleaning in (f) is 4500 revs/min.
Embodiment 2：A kind of porous silicon preparation method, includes the following steps：
(a) the polycrystalline silica flour that 3 parts of particle diameters are 4 μm is measured, uses hydrofluoric acid, sulfuric acid, ethyl alcohol, ultra-pure water eccentric cleaning successively；
(b) by polycrystalline silica flour be put into rubble ice, 4mol/L ammonium hydroxide made of 0.05mol/L stannous sulfates, 20g ultra-pure waters and
It is stirred to react in the mixed solution of 4mol/L hydrofluoric acid 2 minutes, obtains A product；
(c) eccentric cleaning is carried out to A product, obtains B product；
(d) B product are put into the mixed solution of 3mol/L hydrofluoric acid, 0.5% hydrogen peroxide, 3mol/L ammonium hydroxide, 8mL ethyl alcohol, -10
DEG C ice bath stirring corrodes 0.5h, obtains C product；
(e) 0.3mol/L boric acid is added dropwise into C product and 0.5% nitric acid continues to keep -10 DEG C of ice bath stirring corrosion 0.5h, obtains D product；
(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon；
The centrifugal rotational speed of above-mentioned steps (a), (c) and eccentric cleaning in (f) is 3000 revs/min.
Embodiment 3：A kind of porous silicon preparation method, includes the following steps：
(a) the polycrystalline silica flour that 5 parts of particle diameters are 15 μm is measured, uses hydrofluoric acid, sulfuric acid, ethyl alcohol, ultra-pure water eccentric cleaning successively；
(b) polycrystalline silica flour is put into rubble ice, 6mol/L ammonium hydroxide and 6mol/ made of 0.1mol/L stannous sulfates, 50g ultra-pure waters
It is stirred to react in the mixed solution of L hydrofluoric acid 5 minutes, obtains A product；
(c) eccentric cleaning is carried out to A product, obtains B product；
(d) B product are put into the mixed solution of 6mol/L hydrofluoric acid, 3% hydrogen peroxide, 6mol/L ammonium hydroxide, 15mL ethyl alcohol, in 9 DEG C of ice
Bath stirring corrosion 1.5h, obtains C product；
(e) 1.2mol/L boric acid is added dropwise into C product and 1.5% nitric acid continues to keep 9 DEG C of ice bath stirring corrosion 1.5h, obtains D product；
(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon；
The centrifugal rotational speed of above-mentioned steps (a), (c) and eccentric cleaning in (f) is 6000 revs/min.
Claims (5)
1. a kind of porous silicon preparation method, which is characterized in that include the following steps：
(a) the polycrystalline silica flour for measuring 3-5 parts, uses hydrofluoric acid, sulfuric acid, ethyl alcohol, ultra-pure water eccentric cleaning successively；
(b) polycrystalline silica flour is put into 0.05mol/L-O.1mol/L stannous sulfates, 20-50g rubble ices, 4mol/L-6mol/L ammonia
It is stirred to react in the mixed solution of water and 4mol/L-6mol/L hydrofluoric acid 2-5 minutes, obtains A product；
(c) eccentric cleaning is carried out to A product, obtains B product；
(d) B product are put into 3-6mol/L hydrofluoric acid, 0.5%-3% hydrogen peroxide, 3mol/L-6mol/L ammonium hydroxide, 8mL-15mL ethyl alcohol
Ice bath stirring corrodes 0.5h-1.5h in mixed solution, obtains C product；
(e) 0.3mol/L-1.2mol/L boric acid is added dropwise into C product and 0.5%-1.5% nitric acid continues ice bath stirring and corrodes 0.5h-
1.5h obtains D product；
(f) eccentric cleaning is carried out to D product with ultra-pure water, obtains porous silicon.
2. a kind of porous silicon preparation method according to claim 1, it is characterised in that：Polysilicon in the step (a)
The particle diameter of powder is 4-15 μm.
3. a kind of porous silicon preparation method according to claim 1, it is characterised in that：Step (b) medium floe is by surpassing
Pure water is made.
4. a kind of porous silicon preparation method according to claim 1, it is characterised in that：Ice bath in the step (d), (e)
Temperature is -10 DEG C -10 DEG C.
5. a kind of porous silicon preparation method according to claim 1, it is characterised in that：In the step (a), (c) and (f)
The centrifugal rotational speed of eccentric cleaning is 3000-6000 revs/min.
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| CN201810635168.8A CN108483448A (en) | 2018-06-20 | 2018-06-20 | A kind of porous silicon preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109920990A (en) * | 2019-03-01 | 2019-06-21 | 贵州大学 | A kind of microwave prepares silicon-metal-carbon composite preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629736A (en) * | 2016-12-20 | 2017-05-10 | 浙江大学 | Preparation method of porous silicon powder |
| CN106672975A (en) * | 2016-12-20 | 2017-05-17 | 浙江大学 | Preparation method of low-cost nano-porous silica powder |
| CN107572531A (en) * | 2017-10-19 | 2018-01-12 | 贵州大学 | A kind of porous silicon preparation method |
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2018
- 2018-06-20 CN CN201810635168.8A patent/CN108483448A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629736A (en) * | 2016-12-20 | 2017-05-10 | 浙江大学 | Preparation method of porous silicon powder |
| CN106672975A (en) * | 2016-12-20 | 2017-05-17 | 浙江大学 | Preparation method of low-cost nano-porous silica powder |
| CN107572531A (en) * | 2017-10-19 | 2018-01-12 | 贵州大学 | A kind of porous silicon preparation method |
Non-Patent Citations (1)
| Title |
|---|
| HUI ZHENG ET AL.: "Porous silicon templates prepared by Cu-assisted chemical etching", 《MATERIALS LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109920990A (en) * | 2019-03-01 | 2019-06-21 | 贵州大学 | A kind of microwave prepares silicon-metal-carbon composite preparation method |
| CN109920990B (en) * | 2019-03-01 | 2022-02-11 | 贵州大学 | Preparation method for preparing silicon-metal-carbon composite material by microwave |
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Application publication date: 20180904 |