CN104711678A - Method for preparing silicon nanostructure material under alternative electric fields - Google Patents
Method for preparing silicon nanostructure material under alternative electric fields Download PDFInfo
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- CN104711678A CN104711678A CN201510056984.XA CN201510056984A CN104711678A CN 104711678 A CN104711678 A CN 104711678A CN 201510056984 A CN201510056984 A CN 201510056984A CN 104711678 A CN104711678 A CN 104711678A
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Abstract
The invention discloses a method for preparing a silicon nanostructure material under alternative electric fields. The method comprises the following steps: 1, bonding six surfaces of bulk silicon with three pairs of independent inert electrodes, and drilling each of the inert electrodes with a fabrication hole, wherein the inert electrodes can generate alternative electrode fields; 2, putting the bulk silicon obtained in step 1 in a corrosive solution prepared by using hydrofluoric acid, hydrogen peroxide, a metal catalyst and deionized water; and 3, starting the inert electrodes after step 2, controlling the corrosion direction and the corrosion speed under three orthogonal alternative electric fields generated by the three inert electrodes under the frequency of the alternative electric fields of 28-40kHz, taking out the obtained bulk silicon after corrosion for a period of time, and cleaning to prepare the silicon nanostructure material. The method solves the problems of low metal assisted corrosion and low precision of the prepared silicon nanostructure, and controls the corrosion direction through the accurate control of metal catalyst particles by the alternative electric fields in order to realize accurate preparation of the three dimensional silicon nanostructure.
Description
Technical field
The invention belongs to silicon nanostructure technical field of material, be specifically related to a kind of method preparing silicon nanostructure material under alternating electric field.
Background technology
Silicon nanostructure material has a very important role in fields such as semi-conductor industry, sensor, solar cell, MEMS.The method preparing silicon nanostructure material at present mainly contains metal catalytic gas-liquid-solid (VLS) Gu method, solid-liquid-(SLS) growth method, plasma etching method and metal assistant chemical etch etc.Wherein, metal assistant chemical etch rely on easy and simple to handle, do not need the advantages such as precision equipment to obtain in the world extensively to approve and apply.Other method also respectively has advantage.But there is the technical problems such as can not prepare complicated silicon nanostructure material and the structure accuracy of silicon nanostructure material for preparing is not high, preparation efficiency is low in prior art.
Summary of the invention
For prior art Problems existing, the present invention proposes a kind of method preparing silicon nanostructure material under alternating electric field, the method produces action of alternative electric field by three pairs of noble electrodes and assists corrosion process in metal, not only increase the accuracy of corrosion speed and silicon nanostructure, and directional etching direction can be controlled better.
Metal assists noble metal catalyst and silicon face in etch that local galvanic interaction occurs, and its movement locus is processed track.The controllability realizing noble metal catalyst particle also just can good control corrosion position.Extensively approve in the world, in corrosion preparation process, noble metal is with electronegativity, therefore, the present invention adds alternating electric field in the reaction, the movement locus of noble metal granule is guided by electric field controls, thus achieving the direction controllability of silicon nanometer processing, the alternating electric field of 28-40kHz can react front end generation ultrasonic cavitation bubble at precious metal simultaneously, improves directional etching speed.Domestic and in the world all also not about the report of this preparation method at present.
The present invention takes following technical scheme:
Under alternating electric field, prepare a method for silicon nanostructure material, its as follows:
(1), by the body silicon six of cleaning namely all around top and bottom paste three respectively to independently noble electrode, and on each noble electrode, get out a fabrication hole corrosive fluid can be contacted with body silicon, noble electrode produces alternating electric field by electric control gear.The diameter of fabrication hole can be 3-30mm.
(2) the body silicon, step (1) having been pasted noble electrode puts into the good corrosive fluid of proportioning.Corrosive fluid is formulated by hydrofluoric acid, hydrogen peroxide, metal catalyst and deionized water.
(3), after step (2) completes, noble electrode power supply is opened at once.Preparation process is carried out at normal temperatures, and alternating electric field frequency is 28-40kHz, and the three pairs of electrodes produce three orthogonal alternating electric field control corrosion rate directions and corrosion speed by electric control gear.
In the present invention, pilot circuit part and control method belong to prior art, will not describe in detail.
As preferred scheme, the mass concentration of hydrofluoric acid is 40%, the mass concentration 30% of hydrogen peroxide, the volumetric molar concentration 0.2mol/L of Silver Nitrate, and water is deionized water, and corrosive fluid volume ratio is 10:1:1:38 and 12:1:1:36.
As preferred scheme, noble electrode is Graphite Electrodes.
As preferred scheme, nano silicon structure material comprises porous silicon, nano wire, body silicon interior three-dimensional structure.
As preferred scheme, it is 0.001-30 Ω/cm that single crystal silicon material comprises resistivity
2n-type and P type body silicon.
As preferred scheme, electric current is direct current, and strength of electric field is 300v/m-1000v/m.
Step (3), the action of alternative electric field that noble electrode produces, in metal catalyst particles, produces ultrasonic cavitation bubble in corrosive fluid when alternating electric field frequency reaches 28-40kHz, ultrasonic cavitation bubble promotes corrosion speed.
Step (3), the action of alternative electric field that noble electrode produces, in metal catalyst particles, can control corrosion speed.
Comprehensive each influence factor above of the present invention can realize the preparation of multiple silicon nanostructure material, has easy and simple to handle and that integrated level is high advantage, is very applicable to industrialized mass.
The preparation method of silicon nanostructure material of the present invention belongs to silicon nanostructure technical field of material, and it is while metal assists corrosion to prepare silicon nanostructure material, and electronegative metal catalyst particles does mechanical vibration under the effect of alternating electric field; When alternating electric field frequency reaches 28-40kHz, ultrasonic cavitation bubble is produced in corrosive fluid, the effect of ultrasonic cavitation bubble has 2 points: (1), ultrasonic cavitation produce microjet and have strong stirring action to solution, enhance ion to nano silicon structure (as Fine and Deep Hole, nano wire etc.) transportcapacity, maintain corrosive fluid even concentration throughout.(2) ion, in solution is attached to the surface of ultrasonic cavitation bubble, is easy to transfer transport in reaction, accelerates directional etching speed and achieves Siliciumatom chemical and come off; Cavitation bubble produces High Temperature High Pressure in the moment of crumbling and fall, and Siliciumatom physical property is come off.
The inventive method not only solves metal and assists the problems such as corrosion medium-rate silicon nanostructure precision that is low, preparation is low, and by the accurate control of alternating electric field to metal catalyst particles, thus can control corrosion rate direction, realize the accurate preparation of three-dimensional silicon nano structure.
Accompanying drawing explanation
Fig. 1 is the structural representation of body silicon and noble electrode.
Fig. 2 is erosion model under alternating electric field.
Fig. 3 is the monocrystalline silicon nano line structure that the present invention obtains.
Fig. 4 is the body silicon interior three-dimensional nanostructure (the inner semi arch structure of silicon) that the present invention obtains.
Embodiment
Below in conjunction with example, the invention will be further described, but the present invention is not limited to following examples.
In following embodiment, body silicon materials select resistivity to be 0.001-30 Ω/cm
2n-type body silicon or P type body silicon.Hydrofluoric acid mass concentration is 40%, hydrogen peroxide mass concentration 30%, Silver Nitrate volumetric molar concentration 0.2mol/L, and water is deionized water.Electrode is Graphite Electrodes.Material in the present invention is conventional material without specified otherwise, can obtain from commercial channels, and agents useful for same is also regular industrial reagent.
As shown in Figure 1, by the body silicon 2 six of cleaning namely all around top and bottom paste three respectively to independently noble electrode 1,5,3,4, and the fabrication hole getting out a diameter 3-30mm on each noble electrode makes corrosive fluid can contact with body silicon, noble electrode produces alternating electric field by electric control gear.
Embodiment 1, prepare silicon nanowires
Clean body silicon and the noble electrode pasted are put into corrosive fluid, and corrosive fluid component ratio is hydrofluoric acid: hydrogen peroxide: Silver Nitrate: water, volume ratio 12:1:1:36.Connect three pairs of noble electrodes, strength of electric field is 300v/m-1000v/m, and frequency is 40kHz; Take out cleaning corrode 120min at 15 DEG C-25 DEG C after, prepare silicon nanowire structure.
Embodiment 2, prepare silicon nanowires
Clean body silicon and the noble electrode pasted are put into corrosive fluid, and corrosive fluid component ratio is hydrofluoric acid: hydrogen peroxide: Silver Nitrate: water, volume ratio 12:1:1:36.Connect three pairs of noble electrodes, strength of electric field is 300v/m-1000v/m, and frequency is 40kHz; Take out cleaning corrode 120min at 15 DEG C-25 DEG C after, prepare silicon nanowire structure.
Embodiment 3, preparation 3D nano silicon structure (arc structure is prepared in body silicon inside)
Clean body silicon and the noble electrode pasted are put into corrosive fluid, and corrosive fluid component ratio is hydrofluoric acid: hydrogen peroxide: Silver Nitrate: water, volume ratio 10:1:1:38.Three pairs of noble electrodes are opened simultaneously, three respectively strength of electric field be 300v/m-1000v/m, frequency is 28kHz; Take out cleaning corrode 90min at 15 DEG C-25 DEG C after, prepare 3D nano silicon structure.
Embodiment 4, preparation 3D nano silicon structure (arc structure is prepared in body silicon inside)
Clean body silicon and the noble electrode pasted are put into corrosive fluid, and corrosive fluid component ratio is hydrofluoric acid: hydrogen peroxide: Silver Nitrate: water, volume ratio 10:1:1:38.Three pairs of noble electrodes are opened simultaneously, and three Electrode Field intensity are respectively 300v/m-1000v/m, and frequency is 40kHz; Take out cleaning corrode 120min at 15 DEG C-25 DEG C after, prepare 3D nano silicon structure.
See Fig. 2, the process that catalyzer Argent grain is processed in silicon single crystal internal corrosion, catalyzer Argent grain in reaction process, with electronegativity, does simple harmonic oscillation when frequency reaches 28-40kHz under action of alternative electric field, can produce ultrasonic cavitation and steep in catalyzer Argent grain and silicon single crystal contact gap.Cavitation bubble is crumbled and fall and is produced High Temperature High Pressure and impel silicon single crystal physical property to come off, and cavitation bubble attachment ion impels electronics to transfer to catalyzer Argent grain from Siliciumatom, and then transfers in corrosive fluid.Oxidant hydrogen peroxide is reduced to water, and elementary silicon is oxidized to silicon ion.
The present invention is while metal assists corrosion to prepare silicon nanostructure material, electronegative metal catalyst particles is under the effect of applied alternating field, do simple harmonic wave vibration, produce ultrasonic cavitation bubble when alternating electric field frequency reaches 28-40kHz in corrosive fluid and accelerate directional etching speed, alternating electric field can control metal catalyst particles movement path and movement velocity preferably simultaneously, thus can realize the accurate preparation of multiple silicon nanostructure.
Claims (8)
1. under alternating electric field, prepare a method for silicon nanostructure material, its as follows:
(1), six bonding three of body silicon and on each noble electrode, fabrication hole is got out to independently noble electrode, noble electrode can produce alternating electric field;
(2), the body silicon of step (1) is put into by the formulated corrosive fluid of hydrofluoric acid, hydrogen peroxide, metal catalyst and deionized water;
(3), after step (2), open noble electrode, alternating electric field frequency is 28-40kHz, and the three pairs of noble electrodes produce three orthogonal alternating electric field control corrosion rate directions and corrosion speed, cleaning is taken out, obtained silicon nanostructure material after corrosion for some time.
2. under alternating electric field, prepare the method for silicon nanostructure material as claimed in claim 1, it is characterized in that: step (1), the diameter 3-30mm of fabrication hole.
3. under alternating electric field, prepare the method for silicon nanostructure material as claimed in claim 1, it is characterized in that: step (1), noble electrode selects Graphite Electrodes.
4. the method preparing silicon nanostructure material under alternating electric field as described in any one of claim 1-3, is characterized in that: step (1), and body silicon materials select resistivity to be 0.001-30 Ω/cm
2n-type body silicon or P type body silicon.
5. under alternating electric field, prepare the method for silicon nanostructure material as claimed in claim 1, it is characterized in that: step (2), Silver Nitrate selected by metal catalyst.
6. under alternating electric field, prepare the method for silicon nanostructure material as claimed in claim 5, it is characterized in that: step (2), the mass concentration of hydrofluoric acid is 40%, the mass concentration 30% of hydrogen peroxide, the volumetric molar concentration 0.2mol/L of Silver Nitrate.
7. the method preparing silicon nanostructure material under alternating electric field as described in claim 5 or 6, is characterized in that: step (2), and the volume ratio of hydrofluoric acid, hydrogen peroxide, Silver Nitrate, deionized water is 10:1:1:38 or 12:1:1:36.
8. under alternating electric field, prepare the method for silicon nanostructure material as claimed in claim 1, it is characterized in that: step (3), corrode 80-150min at 15 DEG C-25 DEG C after, take out cleaning.
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Cited By (5)
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| CN108328935A (en) * | 2018-04-16 | 2018-07-27 | 中国工程物理研究院激光聚变研究中心 | Alternating electric field auxiliary optical component surface etching treatment device and processing method |
| CN110331427A (en) * | 2019-06-10 | 2019-10-15 | 江苏大学 | A kind of porous silicon-silver nanoparticle pine-tree structure and preparation method thereof |
| CN114348957A (en) * | 2021-12-31 | 2022-04-15 | 杭州电子科技大学 | Equipment for preparing silicon nanostructure by combining alternating electric field with ultrasound |
| CN114605080A (en) * | 2022-04-18 | 2022-06-10 | 广东工业大学 | Method for processing glass through hole based on alternating electric field assistance and etching device |
| CN115787002A (en) * | 2021-09-10 | 2023-03-14 | 东华大学 | Graphene reinforced metal/alloy composite material and preparation method thereof |
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| CN108328935A (en) * | 2018-04-16 | 2018-07-27 | 中国工程物理研究院激光聚变研究中心 | Alternating electric field auxiliary optical component surface etching treatment device and processing method |
| CN108328935B (en) * | 2018-04-16 | 2024-02-27 | 中国工程物理研究院激光聚变研究中心 | Alternating electric field auxiliary optical element surface etching treatment device and treatment method |
| CN110331427A (en) * | 2019-06-10 | 2019-10-15 | 江苏大学 | A kind of porous silicon-silver nanoparticle pine-tree structure and preparation method thereof |
| CN115787002A (en) * | 2021-09-10 | 2023-03-14 | 东华大学 | Graphene reinforced metal/alloy composite material and preparation method thereof |
| CN114348957A (en) * | 2021-12-31 | 2022-04-15 | 杭州电子科技大学 | Equipment for preparing silicon nanostructure by combining alternating electric field with ultrasound |
| CN114605080A (en) * | 2022-04-18 | 2022-06-10 | 广东工业大学 | Method for processing glass through hole based on alternating electric field assistance and etching device |
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