CN102260894A - An electrochemical method for the controllable preparation of silicon nanostructure materials - Google Patents
An electrochemical method for the controllable preparation of silicon nanostructure materials Download PDFInfo
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 31
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 5
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims 1
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims 1
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Abstract
本发明公开了一种制备硅纳米结构材料或其阵列的方法。本发明方法包括下述步骤：以单晶硅为阳极，惰性电极为阴极，将所述阳极和阴极置于电解液中，并向所述电解液中加入与水不混溶的烃类溶剂；在所述阳极施加电流，进行电化学氧化反应，反应结束后得到所述硅纳米结构材料或其阵列；其中，所述电解液由质量浓度为10-30％的氢氟酸溶液、有机溶剂和催化剂组成；所述有机溶剂为甲醇、乙醇或它们任意比例的混合物，所述催化剂为多酸化合物、过氧化氢或它们的混合物；所述与水不混溶的烃类溶剂的密度小于水的密度。该方法通过调节催化剂种类以及电化学反应的电流密度，可实现多种硅纳米结构及其阵列的可控制备，对于硅纳米结构来说是一种通用的制备方法，简单易行。The invention discloses a method for preparing a silicon nanostructure material or an array thereof. The method of the present invention comprises the following steps: using monocrystalline silicon as an anode and an inert electrode as a cathode, placing the anode and the cathode in an electrolytic solution, and adding a water-immiscible hydrocarbon solvent to the electrolytic solution; An electric current is applied to the anode to carry out an electrochemical oxidation reaction, and the silicon nanostructure material or its array is obtained after the reaction; wherein, the electrolyte is composed of a hydrofluoric acid solution with a mass concentration of 10-30%, an organic solvent and Catalyst composition; The organic solvent is methanol, ethanol or their mixture in any proportion, and the catalyst is polyacid compound, hydrogen peroxide or their mixture; The density of the water-immiscible hydrocarbon solvent is less than that of water density. By adjusting the type of catalyst and the current density of electrochemical reaction, the method can realize the controllable preparation of various silicon nanostructures and their arrays, and is a general preparation method for silicon nanostructures, which is simple and feasible.
Description
Technical field
The present invention relates to a kind of electrochemical method of controlled preparation nano structural material.
Background technology
The nanostructure of silicon quantum dot and silicon is considered to the basic structural unit of following electron device, novel luminescent material and catalytic material, has great potential using value at bio-sensing and biomedical sector.Correlative study is significant in nano science and technical field.Because the influence of quantum size effect and dielectric confinement effect, undersized silicon nano have unique photoelectric property, make it demonstrate tempting application prospect at luminous demonstration, laser, illumination, solar cell and biomedical sector.Yet, also exist many problems to need to solve at present in this area research, wherein comparatively outstanding is the controlled and poor repeatability of silicon nanostructure preparation, has the wide shortcoming of yardstick, structure and topographic profile.For the ease of the further application of preparation of silicon-based nano device and silicon nanostructure material, it is very necessary developing a kind of general controlled method for preparing the silicon nanostructure material.
In the nanostructure of silicon, for example the synthetic aspect of porous silicon and silicon quantum dot has report (typical bibliographical information: G.Belomoin, the J.Therrien about electrochemical method, A.Smith, S.Rao, R.Twesten, S.Chaieb, M.H.Nayfeh, L.Wagner, L.Mitas, Appl Phys.Lett.2002,80,841; L.T.Canhum, Appl.Phys.Lett.1990,57,1066; M.H.Nayfeh, N.Barry, J.Therrien, O.Akcakir, E.Gratton, G.Belomoin, Appl.Phys.Lett.2001,78,1131.).But these electrochemical methods can't be realized the controlledly synthesis of multiple silicon nanostructure at present, particularly more lack more accurate control aspect silicon quantum dot synthetic.For the controlled preparation that realizes silicon quantum dot and the controlledly synthesis of multiple silicon nanostructure, develop a kind of general controllable synthesis method and be very important.For the electrochemical method for synthesizing of silicon, the electrochemical corrosion course of silicon is a more complicated, and the interference that also often is subjected to oxygen in the air simultaneously produces side reaction, influences the electrochemical oxidation of silicon chip.Therefore seek and develop a kind of controlled electrochemical system, can control speed and galvanic corrosion orientation that silicon loses electronics, and realize that simultaneously the protection to reaction system is the key issue of realization silicon nanostructure electrochemistry controlledly synthesis.Yet, about the report that yet there are no of the electrochemical reaction system of this aspect.
Summary of the invention
The purpose of this invention is to provide a kind of universal method based on multiple silicon nanostructure of electrochemical controlled preparation and array material thereof.
The method for preparing silicon nanostructure material or its array provided by the present invention, comprise the steps: with silicon single crystal to be anode, noble electrode is a negative electrode, and described anode and negative electrode are placed electrolytic solution, and adds and the immiscible varsol of water in described electrolytic solution; Apply electric current at described anode, carry out electrochemical oxidation reactions, reaction finishes the back and obtains described silicon nanostructure material or its array at described anode; Wherein, described electrolytic solution is that hydrofluoric acid solution, organic solvent and the catalyzer of 10-30% formed by mass concentration; Described organic solvent is the mixture of methyl alcohol, ethanol or their arbitrary proportions, and described catalyzer is polyacid compound, hydrogen peroxide or their mixture; The density of described and the immiscible varsol of water is less than the density of water.
Described noble electrode is meant in electrolyzer, and electrode itself does not participate in the electrode that reacts; For example Graphite Electrodes, gold electrode, platinum electrode etc.
Silicon nanostructure material of the present invention comprises silicon quantum dot (diameter 1-4nm), silicon nano, silicon nanowires, silicon sub-micrometer rod, silicon nano and micropore composite structure, silicon nano-micrometre composite structure (silicon nanorod and micropore composite structure and silicon nanowires and micropore composite structure); Described silicon nanostructure array material comprises silicon micron post array, silicon micron pore array and dendritic silicon nano-structure array.
In the electrolytic solution of the present invention, described organic solvent and mass concentration are that the volume ratio of the hydrofluoric acid solution of 10-30% can be 2: 1-1: 5; Preferred volume ratio is 1: 1-1: 2.
Polyacid compound among the present invention is meant and dissolves in ethanol, methyl alcohol, or the polyoxometallic acid salt compound of aqueous systems, and specifically can be tungsten is that heteropolyacid, molybdenum are heteropolyacid or their mixture.Be typically phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, silicomolybdic acid of 1: 12 serial Keggin structure or 2: 18 serial Dawson structures etc., but be not limited to these.
Described and the immiscible varsol of water be in a liquid state at normal temperatures usually and reactive behavior low, for example low with oxygen reaction or electrochemical reaction activity, wherein aliphatic hydrocarbon is reasonable selection.Specifically can be selected from following at least a: C
6-C
16Alkane, C
6-C
16Naphthenic hydrocarbon and C
6-C
16Alkene.As hexanaphthene, cyclooctane, and n-Hexadecane etc., but be not limited to these.In electrolytic solution, add above-mentioned varsol, can above electrolytic solution, form the organic solvent liquid film.In electrochemical reaction process, this organic liquid film can protect silicon chip not to be subjected to the corrosion of oxygen in the air, and this makes the controllability of solution electrochemistry reaction strengthen.
Silicon single crystal used in the present invention is N type or p type single crystal silicon, and the specific conductivity of described silicon single crystal is 0.005-30 Ω.Employed electrolyzer should be plastic material in the inventive method, or the insulation material that does not react with hydrofluoric acid, as the Teflon, but is not limited to these.
Method of the present invention is to adopt the electrochemical etching method of catalysis pasc reactions such as polyacid compound, hydrogen peroxide, and the organic liquid film guard method in the electrochemical reaction process.After reaction finished, silicon nano material and array structure thereof were retained on the silicon chip or from silicon chip and peel off the interface of getting off to enter electrolytic solution and organic protection layer, were easy to separate or transfer to other solid surface.This method can realize the controlled preparation of multiple silicon nanostructure and array thereof by regulating the current density of catalyst type and electrochemical reaction.
As: in aforesaid method, the catalyzer in the electrolytic solution is selected the mixture of polyacid compound and hydrogen peroxide, and the concentration that makes polyacid compound in the electrolytic solution is 0.01mg/mL-0.03mg/mL, and the mass concentration of hydrogen peroxide is 0.5%-12% (as 0.97%); At 1-20mA/cm
2Current density under, carried out electrochemical oxidation reactions 20-120 minute, can on the anode silicon chip, obtain silicon quantum dot (diameter 1-4nm).
Further improve current density to 20-50mA/cm
2, and adjust the reaction times, and then can obtain the different Nano/micron composite structure of silicon, can obtain silicon nano and micropore composite structure in 0.5-2.5 hour as reaction; Oppositely can obtain silicon nanorod and micropore composite structure in 2.5-5.5 hour; React and to obtain silicon nanowires and micropore composite structure in 5.5-8.5 hour.
If the adjusting catalyst component for example only adds polyacid compound as catalyzer (concentration that makes polyacid compound in the electrolytic solution is 0.01mg/mL-0.1mg/mL), (current density is 1-20mA/cm can to obtain the nanoparticle of silicon
2, reaction times 20-120 minute), (current density is 20-50mA/cm to nano wire
2, reaction times 20-120 minute) and the dendritic silicon nano-structure array (current density is greater than 50mA/cm
2Less than 100mA/cm
2, reaction times 1-3 hour).The silicon nano that obtains, quantum dot and nano wire can obtain monodispersed colloidal particle by supersound process anode silicon chip in methyl alcohol or ethanol.If only adding hydrogen peroxide is catalyzer (concentration that makes hydrogen peroxide in the electrolytic solution is 3%-15%), (current density is 20-50mA/cm can to obtain silicon micron post array
2, reaction times 2-6 hour) and the silicon micron pore array (current density is 20-50mA/cm
2, reaction times 6-9 hour).
Method provided by the present invention is by regulating catalyst type, electrolyte component, and the current density of electrochemical reaction can realize the controlled preparation of multiple silicon nanostructure and array thereof, and easy to operation, is a kind of general preparation method for silicon nanostructure.
Description of drawings
The diameter that Fig. 1 prepares for embodiment 1 is the silicon quantum dot electromicroscopic photograph of 1,2,3,4 nanometers.
The diameter that Fig. 2 prepares for embodiment 2 is the electromicroscopic photograph of the silicon nano of 30 nanometers.
The diameter that Fig. 3 prepares for embodiment 3 is the electromicroscopic photograph of the silicon nanowires of 30-80 nanometer.
The silicon nano that Fig. 4 obtained for reaction among the embodiment 4 in 1 hour and the electromicroscopic photograph of micropore composite structure.
The silicon nanorod that Fig. 5 obtained for reaction among the embodiment 4 in 3-5 hour and the electromicroscopic photograph of micropore composite structure.
The silicon nanowires that Fig. 6 obtained for reaction among the embodiment 4 in 7 hours and the electromicroscopic photograph of micropore composite structure.
The electromicroscopic photograph of the silicon micron pillar array structure that Fig. 7 prepares for embodiment 5.
The electromicroscopic photograph of the silicon micron pore array structure that Fig. 8 prepares for embodiment 6.
The electromicroscopic photograph of the dendritic silicon nano-structure array that Fig. 9 prepares for embodiment 7.
Embodiment
The present invention adopts electrochemical method; by organic liquid film to the protection of reaction system, control current density, regulate means such as catalyst component, controlling reaction time; realize controlled preparation silicon quantum dot (diameter 1-4 nanometer), silicon nano, silicon nanowires, and multiple silicon nanostructure and array structure thereof such as silicon Nano/micron composite structure.
Below by specific embodiment method of the present invention is described, but the present invention is not limited thereto.Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.20% and 5% hydrofluoric acid solution can be diluted in proportion through deionized water by commercial hydrofluoric acid solution (35-48%) and obtain among the embodiment." % " concentration described in the following embodiment is " mass percentage concentration ".
With mass concentration is that 95% ethanolic soln, mass concentration are that 20% hydrofluoric acid solution and mass concentration be 30% hydrogen peroxide according to volume ratio are to mix at 2: 1: 0.1, add phospho-wolframic acid, making the concentration of phospho-wolframic acid in the electrolytic solution is 0.02mg/mL, obtains being used to prepare the electrolytic solution of silicon quantum dot after stirring.
P type silicon chip (specific conductivity 0.005-30 Ω, reaction area 0.5-1cm
2) be 5% hydrofluoric acid dips 2-5 minute with mass concentration, to use successively then behind ethanol, the distilled water flushing as anode, graphite rod is as negative electrode.Get 100ml electrolytic solution and place plastic electrobath, and in described electrolytic solution (reaction system), add 30 milliliters of hexanaphthenes, above electrolytic solution, form the organic solvent liquid film.At 15-20mA/cm
2Current density under, carried out electrochemical oxidation reactions 30 minutes, on the anode silicon chip, obtain silicon quantum dot, its diameter is about 1nm, after the electrochemical reaction, can obtain monodispersed silicon quantum dot by supersound process anode silicon chip in methyl alcohol or ethanol, electromicroscopic photograph is seen Fig. 1 a.Reduce the current density of electrochemical reaction, can obtain the different silicon quantum dot of diameter, specific as follows: current density is 8-12mA/cm
2, 5-8mA/cm
2, 1-5mA/cm
2The time to obtain diameter respectively be 2,3, the silicon quantum dot of 4nm.Electromicroscopic photograph is seen accompanying drawing 1b-1d.
Embodiment 2, preparation silicon nano
95% ethanolic soln is mixed according to 1.5: 1 ratio of volume ratio with 20% hydrofluoric acid solution, add phospho-molybdic acid, making the concentration of phospho-molybdic acid in the electrolytic solution is 0.03mg/mL, obtains being used to prepare the electrolytic solution of silicon quantum dot after stirring.Silicon chip (specific conductivity 0.005-30 Ω, reaction area 0.5-1cm
2) with 5% hydrofluoric acid dips 2-5 minute, use successively then behind ethanol, the distilled water flushing as anode, graphite rod is as negative electrode.Get 100ml electrolytic solution and place plastic electrobath, and in described electrolysis, add the 30ml hexanaphthene, above electrolytic solution, form the organic solvent liquid film.At 15-20mA/cm
2Current density under, carried out electrochemical oxidation reactions 30 minutes, on the anode silicon chip, obtain silicon nano, its diameter is about 30 nanometers.After the reaction, can obtain monodispersed silicon nano by supersound process anode silicon chip in methyl alcohol or ethanol, electromicroscopic photograph is seen Fig. 2, and a-d is the different figure electromicroscopic photograph of magnification among the figure.
Embodiment 3, preparation silicon nanowires
Method according to embodiment 2 is prepared, but the current density of change reaction is 20-50mA/cm
2, carried out electrochemical redox reaction 30-60 minute, on the anode silicon chip, obtain silicon nanowires, its diameter is about the 30-80 nanometer.After the reaction, can obtain monodispersed silicon nanowires by supersound process anode silicon chip in methyl alcohol or ethanol, electromicroscopic photograph is seen accompanying drawing 3.Illustration among Fig. 3 a is a partial enlarged drawing, and the top illustration is an electron diffraction pattern among Fig. 3 b, and the below illustration is the high-resolution electron microscopy photo.
Embodiment 4, preparation silicon Nano/micron composite structure
Method according to embodiment 1 is prepared, but the current density of change reaction is 20-50mA/cm
2Carried out electrochemical redox reaction 1-7 hour, and on the anode silicon chip, can obtain silicon nano and micropore composite structure respectively.In 1 hour reaction times, the electromicroscopic photograph of gained silicon nano and micropore composite structure is seen Fig. 4, three electromicroscopic photographs that electromicroscopic photograph is a different amplification among Fig. 4, and the lower right is a distribution diagram of element.Reaction times 3-5 hour, the electromicroscopic photograph of gained silicon nanorod and micropore composite structure was seen Fig. 5.In 7 hours reaction times, the electromicroscopic photograph of gained silicon nanowires and micropore composite structure is seen Fig. 6.
Embodiment 5, preparation silicon micron pillar array structure
Is to mix at 2: 1: 0.5 95% ethanolic soln, 20% hydrofluoric acid (HF) solution and 30% superoxol according to volume ratio, obtains needed electrolytic solution after stirring.Silicon chip (specific conductivity 0.005-30 Ω, reaction vector product 0.5-1cm
2) with 5% hydrofluoric acid dips 2-5 minute, use successively then behind ethanol, the distilled water flushing as anode, graphite rod is as negative electrode.Get 100ml electrolytic solution and place plastic electrobath, and in described electrolysis, add 30 milliliters of hexanaphthenes, above electrolytic solution, form the organic solvent liquid film.At 20-50mA/cm
2Current density under, carried out electrochemical oxidation reactions 5 hours, on the anode silicon chip, obtain silicon submicron pillar array structure, electromicroscopic photograph is seen Fig. 7.
Embodiment 6, preparation silicon micron pore array structure
Method according to embodiment 5 is prepared, but improves the electrochemical oxidation reactions time, increases to 7 hours, obtains silicon micron pore array structure on the anode silicon chip, and electromicroscopic photograph is seen Fig. 8.
Embodiment 7, preparation dendritic silicon nano-structure array
Method according to embodiment 2 is prepared, but the current density of change reaction is greater than 50mA/cm
2Less than 100mA/cm
2, carried out electrochemical redox reaction 1-3 hour, on the anode silicon chip, obtain silicon dendritic silicon nano-structure array, electromicroscopic photograph is seen accompanying drawing 9.
Among any one above-mentioned embodiment, ethanolic soln can be replaced with the mixing solutions of methyl alcohol or methyl alcohol and ethanol arbitrary proportion.
Among any one above-mentioned embodiment, the organic solvent hexanaphthene can be replaced C
6-C
16Any alkane, alkene or its mixture, require density or proportion proportion less than water.
Among any one above-mentioned embodiment, the polyacid catalyzer can be replaced with phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, silicomolybdic acid, germanotungstic acid, germanium molybdic acid of 1: 12 serial Keggin structure or 2: 18 serial Dawson structures etc.
Among any one above-mentioned embodiment, hydrofluoric acid solution concentration can be the arbitrary value between the 10%-30%, comprises final condition, is good with 20%.
Claims (10)
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| CN103754880A (en) * | 2014-01-20 | 2014-04-30 | 复旦大学 | Large-scale production method of silicon quantum dots |
| CN104928743A (en) * | 2015-06-24 | 2015-09-23 | 西安航空动力股份有限公司 | Preprocessing method for inspecting monocrystalline completeness of monocrystalline turbine blades |
| CN106744670A (en) * | 2016-11-23 | 2017-05-31 | 杭州电子科技大学 | A kind of method that silicon nanostructure is prepared under electromagnetic coupled field action |
| CN110225890A (en) * | 2015-12-04 | 2019-09-10 | 小林光 | The hydrogen containing hydrogen solution, the manufacturing method containing hydrogen solution, the manufacturing device containing hydrogen solution and living body generates material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754880A (en) * | 2014-01-20 | 2014-04-30 | 复旦大学 | Large-scale production method of silicon quantum dots |
| CN104928743A (en) * | 2015-06-24 | 2015-09-23 | 西安航空动力股份有限公司 | Preprocessing method for inspecting monocrystalline completeness of monocrystalline turbine blades |
| CN104928743B (en) * | 2015-06-24 | 2017-04-19 | 西安航空动力股份有限公司 | Preprocessing method for inspecting monocrystalline completeness of monocrystalline turbine blades |
| CN110225890A (en) * | 2015-12-04 | 2019-09-10 | 小林光 | The hydrogen containing hydrogen solution, the manufacturing method containing hydrogen solution, the manufacturing device containing hydrogen solution and living body generates material |
| CN106744670A (en) * | 2016-11-23 | 2017-05-31 | 杭州电子科技大学 | A kind of method that silicon nanostructure is prepared under electromagnetic coupled field action |
| CN106744670B (en) * | 2016-11-23 | 2019-01-29 | 杭州电子科技大学 | A method of silicon nanostructure is prepared under electromagnetic coupling field action |
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