CN106672974A - New method for preparing silicon micro-nano hierarchical structure - Google Patents
New method for preparing silicon micro-nano hierarchical structure Download PDFInfo
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- CN106672974A CN106672974A CN201611160207.0A CN201611160207A CN106672974A CN 106672974 A CN106672974 A CN 106672974A CN 201611160207 A CN201611160207 A CN 201611160207A CN 106672974 A CN106672974 A CN 106672974A
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a new method for preparing a silicon micro-nano hierarchical structure. The method comprises the following steps: S1, putting a cleaned silicon slice into a mixed solution of potassium hydroxide and isopropanol in a heating and stirring state to be etched, so as to obtain a pyramid-shaped silicon micro structure array uniform in size and distribution; S2, integrating an adhesion layer/silver nano film on the surface of the pyramid-shaped silicon micro structure array; S3, putting a sample treated by the step S2 into a salt solution containing halide ions, and carrying out pitting reaction, so as to obtain island-shaped silver particles or a porous silver film; and S4, putting the sample treated by the step S3 into a mixed solution of hydrofluoric acid and hydrogen peroxide to be etched, so that a novel silicon micro-nano hierarchical structure is obtained. The preparation method has the advantages of low cost, simple operation and controllable process and is applicable to large-scale production, and the obtained novel silicon micro-nano structure has a very large effective surface area and an extremely strong practical value, thereby being worthy of popularization in the industry.
Description
Technical field
The invention belongs to micro-nano structure manufacturing technology field, and in particular to a kind of new side for preparing silicon micro-nano hierarchy
Method.
Background technology
With the fast development of micro-/nano electromechanical systems, for example miniature lithium ion battery of micro- energy device etc. is greatly closed
Note.Silicon micro-nano structure can be widely used in the devices such as miniature lithium ion battery and photovoltaic solar cell, it may also be used for photoelectric transfer
In sensor.The most frequently used preparation method of silicon micro-nano structure is metal catalytic etching and reactive ion etching.Reactive ion etching work
Skill needs expensive equipment, such as sense coupling machine or reactive ion etching machine, thus processing cost is higher.And
Metal catalytic etching technics prepares the advantage that silicon micro-nano structure has low cost.Metal catalytic etching technics is referred to gold or silver etc.
Noble metal nano particles are deposited on silicon chip surface, then put it into perform etching in Fluohydric acid. and the mixed solution of hydrogen peroxide so as to
Obtain silicon nanostructure.Noble metal nano particles play during the course of the reaction catalysis, have the region of metal nanoparticle anti-
Should be violent, silicon structure is removed；Region silicon structure without metal nanoparticle is stayed, so as to form silicon micro-nano structure.Your gold
Metal nano-particle becomes the key for preparing silicon micro-nano structure, and its pattern and feature directly affect the generation of silicon micro-nano structure.It is conventional
Noble metal nano particles preparation method include plating film combination annealing obtaining island metal nanoparticle, or utilize reactive ion
The pipe/polyhenylethylene nano bead template that etching technics etching metallic film is covered is so as to obtain metal nanoparticle.It is possible with silver
Mirror reaction generates nanometer silverskin, and the catalyst for being used as metal catalytic etching is put in hydrofluoric acid solution and performs etching and obtain
Silicon micro-nano structure.
Metal nano spot corrosion is a common failure phenomenon, wishes to be avoided as much as nano dot in actual applications
Erosion.If nanometer spot corrosion can be introduced in micro-nano structure manufacture, the new side of development low cost and prepare with scale micro-nano hierarchy
Method, will be very meaningful.The present invention proposes, nanometer spot corrosion is combined with metal catalytic etching technics, can prepare silicon micro-nano and be classified
Structure.Inventor's research discovery, chromium plating/silver nanoparticle thin film in flat silicon substrate, then nano dot is carried out to it with halide ion
Erosion, with reference to metal catalytic etching silicon nanowire structure is obtained.If integrated chromium/silver nanoparticle thin film on silicon microstructure array, knot
The spot corrosion of halide ion nanometer and metal catalytic etching technics are closed, lamellar or other novel silicon micro-nano hierarchies can be obtained.
The content of the invention
The present invention is based on metal nano spot corrosion phenomenon, there is provided a kind of simple, the with low cost silicon micro-nano hierarchy of process
Preparation method.
The technical scheme is that：A kind of new method for preparing silicon micro-nano hierarchy, comprises the following steps：
S1, prepare silicon microstructure array：In 80~100 DEG C of water bath, the silicon chip for cleaning up is put into and is in
In the potassium hydroxide of stirring and the mixed solution of isopropanol, it is performed etching, obtain pyramid silicon microstructure array；
S2, integrated silver nanoparticle thin film：The pyramid silicon microstructure array surface obtained in step S1 deposits one layer of adhesion
Layer, then integrated silver nanoparticle thin film；
S3, spot corrosion silver nanoparticle thin film：Sample after the process of step S2 is put in the saline solution containing halide ion,
Spot corrosion reaction is carried out, porous silverskin is obtained；
S4, prepare silicon micro-nano hierarchy：Sample after the process of step S3 is put into into Fluohydric acid. and hydrogen peroxide
In mixed solution, it is performed etching, obtain silicon micro-nano hierarchy.
In above-mentioned technical proposal, step can also be included：S0, cleaning silicon chip：It is 85~120 DEG C that silicon chip is put into into temperature
10~20min is cleaned in the mixed solution of ammonia and hydrogen peroxide, is rinsed well repeatedly using deionized water after taking-up.Further
, ammonia, hydrogen peroxide, the volume ratio of deionized water are 1：1：5.The main purpose of step S0 is to obtain the silicon for cleaning up
Piece, removes impurities on surface of silicon chip, it is to avoid the technological operation such as etching in subsequent step is impacted.Ammonia, hydrogen peroxide, deionization
The ratio of water is adjusted also dependent on needs, thus all under the guidance of inventive concept, clear using this area conventional silicon wafers
Other methods in washing method are fallen within protection scope of the present invention.
In above-mentioned technical proposal, in step S1, find in research process, using potassium hydroxide silicon pyramid is etched
In type configuration process, if etching liquid remains static, resulting silicon microstructure size and distribution is all uneven.Make mixing molten
Purpose of the liquid in stirring is to keep solution uniformly to mix in etching process, while the bubble produced by etching structure can
It is quick to exclude, it is more beneficial for obtaining equally distributed pyramid silicon microstructure array.If speed of agitator is too low, bubble cannot and
When be discharged to sample surfaces, the homogeneity of etching structure pattern will be had influence on；If speed of agitator is too high, stirring can acutely affect very much knot
The generation of structure.Preferred 100rpm~the 800rpm of speed of agitator.Further, can select but be not limited to magnetic agitation or machinery is stirred
Mix.Because magneton or stirring paddle can closely affect very much the pattern of etching process and silicon microstructure apart from sample.Thus work as and stirred using machinery
When mixing, preferred stirring paddle is arranged at sample top apart from sample 20mm~50mm.When using magnetic agitation, preferred magneton and sample
The distance between product are 10mm~30mm.Additionally, further preferably the ratio of isopropanol and deionized water is 1：4, potassium hydroxide
Concentration range be 20%~60%, the preferred 20min~40min of etch period.After the completion of etching, sample is taken out, use deionization
Dried up with nitrogen gun again after water rinse.Perusal can find pyramid silicon microstructure sample in uniform furvous,
If solution is not stirred in etching process obtained color sample is uneven, some field color are dark, some regions
Color is brighter.
In above-mentioned technical proposal, the coating process of step S2 can be selected but be not limited to magnetron sputtering, electron beam and steam
Send out or electroplating technology.Before integrated silver nanofilm, in micro-structure surface one layer of adhesion layer is plated, with strengthen nanometer spot corrosion reaction and
Adhesiveness during metal catalytic etching reaction between silverskin and silicon substrate.Adhesion layer is that the adhesiveness of 1nm~5nm is preferable
Metal film, such as titanium, chromium, nickel and titanizing tungsten nanometer film.The thickness of silver nanoparticle thin film is 30nm~100nm.Carve in metal catalytic
During erosion, adhesion layer is etched away rapidly by Fluohydric acid., and afterwards silverskin and silicon substrate directly contact are so as to performing etching reaction.
The specific process parameter that plated film is related to can directly using this area conventional parameter and mode of operation, and it is special that the present invention has no to this
Restriction.The thickness of the integrated silver nanoparticle thin film in this place can affect the silicon micro-nano hierarchy pattern for finally obtaining.Nanometer silver
When film is relatively thin, silver-colored island grain structure is formed after spot corrosion reaction, obtained on silicon microstructure surface after metal catalytic etching reaction
To silicon nanowire structure；When silverskin is thicker, porous silverskin structure is formed after same time spot corrosion, in metal catalytic etching
Silverskin structure has larger stress in course of reaction, and four faceted pebbles of silicon microstructure are etched under stress, obtain silicon
Micro-nano hierarchy.Therefore for the thickness of silver nanoparticle thin film can be adjusted according to the actual requirements.
In above-mentioned technical proposal, in step S3, inventor's research finds, corrosion process of the halide ion to silver nanoparticle thin film
In, the concentration of etching time and halide ion is very crucial.If etching time mistake of the halide ion of low concentration to silver nanoparticle thin film
Short, spot corrosion reaction is relatively slower, and the silver nanoparticle thin film hole for obtaining is less so that it cannot be obtained in subsequent catalyst etch step
Silicon micro-nano hierarchy；If halogen ion concentration is high and etching time is long, the porous silverskin for obtaining is sparse, and silver nanoparticle
Thin film has the risk for departing from silicon substrate.Therefore, the concentration of chloride ion is preferably 0.1mol/L~2mol/L, and the spot corrosion response time is excellent
Elect 5min~30min as, good corrosive effect can be reached.After the completion of reaction, sample is taken out and is put in deionized water
Rinse, dry up.The saline solution of halide ion refers to the saline solution containing halide ions such as fluorine, chlorine, bromine, iodine, such as potassium chloride, chlorine
Change sodium, potassium fluoride, potassium bromide, potassium iodide etc..
In above-mentioned technical proposal, in step S4, preferred etch period is 3min~40min.It is rotten by halide ion
The porous silverskin that erosion silver nanoparticle thin film is obtained plays a part of catalyst in etching process.In etching process, porous silverskin with
Stress between pyramid silicon microstructure causes structure to start to generate along pyramidal four faceted pebbles, with the change of stress
Change, silicon microstructure surface defines the silicon micro-nano structure of one one.It is anti-that the shape of gained silicon micro-nano structure depends primarily on spot corrosion
Stress state in the porous silverskin pattern that should be obtained afterwards and etching process.After the completion of etching, using deionized water rinse sample
Product, then put it into and etch in concentrated nitric acid 2min~5min to remove the silver nanoparticle thin film of remained on surface, reuse deionized water
After rinse.
The invention has the beneficial effects as follows：What the present invention was provided prepares the new method of silicon micro-nano hierarchy, combining hydrogen oxidation
Potassium etching, integrated silver nanoparticle thin film, spot corrosion silver nanoparticle thin film and silver are catalyzed the techniques such as etching, prepare novel silicon micro-nano classification knot
Structure.During the technique for preparing pyramid silicon microstructure is etched in potassium hydroxide, stirring technique is introduced in etching process, makes etching
Liquid uniformly mixes and discharges bubble rapidly, to obtain uniform silicon microstructure array.Additionally, dexterously nanometer spot corrosion is introduced into micro-
In micro-nano structure manufacture, silver nanoparticle thin film is corroded so as to form porous silver nanofilm structure using halide ion, by itself and silver catalysis
Etching is carried out effectively combining and prepares silicon micro-nano hierarchy.Not yet to have at present be used for metal nano spot corrosion and prepare the classification of silicon micro-nano
The technology precedent of structure.And silver nanoparticle thin film only need to be placed in the saline solution of halogen-containing ion by obtaining for porous silver nanofilm
Row spot corrosion.
In general, the preparation method has the advantages that low cost, simple to operate, process control, is suitable to large-scale production,
Gained novel silicon micro-nano structure has very big effective surface area, has in the field such as micro- energy device and micro sensing device wide
Wealthy application prospect, with extremely strong practical value, is worth being promoted in interior industry.
Description of the drawings
Fig. 1 is the process chart for preparing silicon micro-nano hierarchy proposed by the present invention；
Fig. 2 is the pyramid silicon microstructure array SEM figures obtained in embodiment one, wherein (a) is conventional potassium hydroxide
Pyramid silicon microstructure array SEM figures obtained by etching, are (b) that stirring technique gained pyramid silicon is introduced in etching process
Micro structure array SEM schemes；
Fig. 3 is silicon micro-nano hierarchy SEM figures prepared by embodiment one, wherein (a) is the SEM figures of 5000 times of amplification, (b)
It is the SEM figures of 10000 times of amplification；
Fig. 4 is silicon micro-nano hierarchy SEM figures prepared by example IV, wherein (a) is the SEM figures of 10000 times of amplification,
B () is the SEM figures of 30000 times of amplification.
Description of reference numerals：1st, silicon substrate；2nd, pyramid silicon microstructure array；3rd, silver nanoparticle thin film；4th, porous nano
Silverskin；5th, silicon micro-nano hierarchy.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.
As shown in figure 1, the preparation technology flow chart of the present invention, after processing respectively through step S0 clean silicon substrate is obtained
1, uniform pyramid silicon microstructure array 2 is obtained after the process of step S1, the nanometer thin obtained Jing after the process of step S2
Film 3, the porous silver nanoparticle thin film obtained Jing after the process of step S3 obtains silicon micro-nano hierarchy Jing after the process of step S4, above-mentioned
Step is specially：
S0, cleaning silicon chip：Silicon chip is put into into temperature for 85 DEG C~120 DEG C, volume ratio is 1:1:5 ammonia：Hydrogen peroxide：Go
10min~30min is cleaned in ion water mixed solution, is then rinsed well repeatedly using deionized water, and dried up with nitrogen gun.
S1, prepare silicon microstructure array：In 80~100 DEG C of water bath, the silicon chip for cleaning up is put into and is in
It is performed etching in the potassium hydroxide and isopropyl alcohol mixture of stirring, the ratio of isopropanol and deionized water is 1：4,
The mass concentration scope of potassium hydroxide is 20%~60%, and whipping step is introduced in etching process, and rotating speed is set to 100rpm
~800rpm, etch period is 20min~40min, obtains pyramid silicon microstructure array；
S2, integrated silver nanoparticle thin film：The pyramid silicon microstructure array surface obtained in step S1 is plated a layer thickness and is
The adhesion layer (usually titanium titanium, chromium, nickel and titanizing tungsten nanometer film etc.) of 1nm~5nm, then integrated thickness is for 30nm~100nm's
Silver nanoparticle thin film；
S3, spot corrosion silver nanoparticle thin film：Sample after the process of step S2 is put in the saline solution containing halide ion,
Carry out spot corrosion reaction, keep 10min~30min, take out sample and be put in deionized water rinse and dry up, obtain porous silverskin；
S4, prepare silicon micro-nano hierarchy：Sample after the process of step S3 is put into into Fluohydric acid. and hydrogen peroxide
In mixed solution, 3min~40min is performed etching to it, deionized water rinse is taken out afterwards, be then placed in being carved in concentrated nitric acid
Erosion 2min~5min, reuses acquisition silicon micro-nano hierarchy after deionized water rinse.
The present invention is described in further detail below by way of specific embodiment, further to show that the present invention's is excellent
Point and principle：
Embodiment one
S0, cleaning silicon chip：It is 1 that monocrystal silicon (100) substrate is put into into temperature for 85 DEG C, volume ratio：1：5 ammonia：Dioxygen
Water：10min is cleaned in deionized water mixed solution, is taken out use a large amount of deionized water rinsings afterwards, and dried up with nitrogen gun.
S1, prepare silicon microstructure array：In 85 DEG C of water bath, by the silicon chip for cleaning up be put into potassium hydroxide and
In the mixed solution of isopropanol, etching liquid includes 80ml deionized waters, 20ml isopropanols (analysis is pure) and 3.09g potassium hydroxide
(analysis is pure).Etching liquid is stirred using magnetic agitation mode, rotating speed is set to 400rpm.Magneton can not connect with sample
Touch, the distance between magneton and sample are set to into~10mm.Etching reaction can be observed in etching process acutely, there are a large amount of gas
Bubble is produced, and bubble is discharged rapidly along with the agitation of solution.Through etching, size and the pyramid being evenly distributed can be obtained
Type silicon microstructure array.
The pyramid silicon microstructure array SEM figures obtained in the present embodiment are illustrated in figure 2, wherein (a) is conventional hydrogen
Potassium oxide etching gained pyramid silicon microstructure array SEM figures, are (b) that stirring technique gained pyramid is introduced in etching process
Type silicon microstructure array SEM schemes.It is seen that the silicon microstructure size in (a) figure differs, and the region having does not have
Etch silicon microstructure；B the silicon microstructure in () figure is uniformly distributed, and the size of structure is also more uniform.
S2, integrated silver nanoparticle thin film：The pyramid obtained in step S1 using magnetron sputter (BEIYI JPGF 700A)
Titanium deposition/silver nanoparticle thin film in type silicon microstructure array surface.The thickness of adhesion layer-titanium nanometer film is 2nm.Magnetron sputtering process
In, using rf-mode, air pressure is set to 0.2Pa, and power setting is 100W.After build-up of luminance, first baffle plate is covered into sample about 3min,
Baffle plate is removed after oxide layer removal Deng target material surface.Plated film time is set to 50s, and the silver nanoparticle film thickness for obtaining is about
50nm。
S3, spot corrosion silver nanoparticle thin film：The pyramid silicon microstructure array for being coated with titanium/silver nanoparticle thin film is put into into concentration is
In the Klorvess Liquid of 0.1mol/L, spot corrosion reaction 10min is carried out, sample is taken out afterwards and is put in deionized water rinse and is blown
It is dry, obtain porous silverskin-pyramid silicon microstructure array；
S4, prepare silicon micro-nano hierarchy：Porous silverskin-pyramid silicon microstructure that step S3 is obtained is put into into hydrogen fluorine
Acid and hydrogen peroxide mixed solution in, solution comprising 1.225ml hydrogen peroxide (30%), 22.33ml Fluohydric acid .s (40%) and
76.445ml deionized waters.Titanium adhesion layer is removed by rapid etching, and afterwards silverskin starts to be catalyzed and carves with silicon microstructure directly contact
Erosion, after reaction 20min sample deionized water rinse sample is taken out, and is placed into and etch in concentrated nitric acid the silver that 2min removes residual
Film, afterwards deionized water rinse again obtains silicon micro-nano hierarchy.
As shown in figure 3, be silicon micro-nano hierarchy SEM figures manufactured in the present embodiment, wherein (a) is to amplify 5000 times
SEM schemes, and (b) is the SEM figures of 10000 times of amplification.It is seen that the entirety of gained silicon micro-nano hierarchy is lamellar (class
It is similar to Musa basjoo Sieb. Et Zucc. lobate) array, but the silicon nanowires of many points of row can be seen in body structure surface.
Embodiment two
The present embodiment is compared with embodiment one, except step S1 is slightly different, remaining step all same.Step in the present embodiment
S1 is specially：
S1, prepare silicon microstructure array：In 85 DEG C of water bath, by the silicon chip for cleaning up be put into potassium hydroxide and
In the etching liquid of isopropanol, etching liquid includes 80ml deionized waters, 20ml isopropanols (analysis is pure) and 3.09g potassium hydroxide.Adopt
Etching liquid is stirred with the mode of mechanical agitation (OA2000, Shanghai Ou He plant equipment company limited), rotating speed is set to
600rpm, stirring paddle is arranged on sample top, is 20mm or so apart from sample.Etching reaction can be observed in etching process acute
It is strong, there are a large amount of bubbles to produce, due to the carrying out stirred, bubble is discharged rapidly.After etching reaction carries out 30 minutes, sample is taken out
Dried up with nitrogen gun after deionized water rinse, pyramid silicon microstructure array can be obtained.
Embodiment three
The present embodiment is compared with embodiment one, except step S2 is slightly different, remaining step all same.Step in the present embodiment
S2 is specially：
S2, integrated silver nanoparticle thin film：Using resistance-type thermal evaporation plated film instrument (Wuhan Na Mei Science and Technology Ltd.s) in step
The integrated titanium of pyramid silicon microstructure array surface/silver nanoparticle thin film that S1 is obtained.In coating process, the thickness of titanium nanometer film is
2nm.During silver-plated nano thin film, the vacuum of plated film instrument is set to 10-4Pa, electric current is set to 110A, and deposit thickness is about 50nm
Silver nanoparticle thin film.
Example IV
Compared with embodiment one, silver nanoparticle film thickness integrated in step S2 is different, and remaining step is equal for the present embodiment
It is identical.
S2, integrated silver nanoparticle thin film：The pyramid obtained in step S1 using magnetron sputter (BEIYI JPGF 700A)
Deposition of silver nano thin-film in type silicon microstructure array surface.In magnetron sputtering process, using rf-mode, air pressure is set to
0.2Pa, power setting is 100W.After build-up of luminance, first baffle plate is covered into sample about 3min, after waiting the oxide layer of target material surface to remove
Remove baffle plate.Plated film time is set to 30s, and the silver nanoparticle film thickness for obtaining is about 30nm.
Different patterns are had based on the preparation-obtained silicon micro-nano hierarchy of 30nm silver nanoparticle thin film.As shown in figure 4,
A () figure is the SEM figures that amplification is 10000 times, (b) figure is the SEM figures that amplification is 30000 times.It is seen that
Due to the thinner thickness of silver nanoparticle thin film, there is the silver-colored structure that island is formed after nanometer spot corrosion reaction, etch through metal catalytic,
Vertical silicon nanowire structure is formed on silicon microstructure surface.
Embodiment five
The present embodiment is compared with embodiment one, except step S3 is slightly different, remaining step all same.Step in the present embodiment
S3 is specially：
S3, spot corrosion silver nanoparticle thin film：The pyramid silicon microstructure array for being coated with silver nanoparticle thin film is put into into concentration is
In the sodium bromide solution of 0.2mol/L, spot corrosion reaction 10min is carried out, sample is taken out afterwards and is put in deionized water rinse and is blown
It is dry, obtain porous silverskin-pyramid silicon microstructure array.
One of ordinary skill in the art will be appreciated that embodiment described here is to aid in reader and understands this
Bright principle, it should be understood that protection scope of the present invention is not limited to such especially statement and embodiment.This area
It is each that those of ordinary skill can make various other without departing from essence of the invention according to these technologies enlightenment disclosed by the invention
Plant concrete deformation and combine, these deformations and combination are still within the scope of the present invention.
Claims (10)
1. a kind of new method for preparing silicon micro-nano hierarchy, it is characterised in that comprise the following steps：
S1, prepare silicon microstructure array：In 80~100 DEG C of water bath, the silicon chip for cleaning up is put in stirring
Perform etching in the potassium hydroxide and isopropyl alcohol mixture of state, obtain pyramid silicon microstructure array；
S2, integrated silver nanoparticle thin film：After the pyramid silicon microstructure array surface that step S1 is obtained deposits one layer of adhesion layer,
Again in the integrated silver nanoparticle thin film in its surface；
S3, spot corrosion silver nanoparticle thin film：The sample processed through step S2 is put in the saline solution containing halide ion, is carried out a little
Erosion reaction, obtains porous silverskin；
S4, prepare silicon micro-nano hierarchy：Sample after the process of step S3 is put into into the mixing of Fluohydric acid. and hydrogen peroxide
In solution, it is performed etching, obtain novel silicon micro-nano hierarchy.
2. the new method for preparing silicon micro-nano hierarchy according to claim 1, it is characterised in that：In step S2
Adhesion layer is metal film, and thickness is 1~5nm.
3. the new method for preparing silicon micro-nano hierarchy according to claim 2, it is characterised in that：The metal film is titanium
One kind in nanometer film, chromium nanometer film, nickel nanometer film or titanizing tungsten nanometer film.
4. the new method for preparing silicon micro-nano hierarchy according to claim 1, it is characterised in that：In step S4,
After the completion of etching, using deionized water to sample rinse after, be put in concentrated nitric acid and etch 2~5min to remove the silver of remained on surface
Nano thin-film, reuses deionized water rinse.
5. the new method for preparing silicon micro-nano hierarchy according to claim 1, it is characterised in that：In step S1,
The range of speeds is controlled for 100rpm~800rpm.
6. the new method for preparing silicon micro-nano hierarchy according to claim 1, it is characterised in that：In step S1,
The mass concentration scope of potassium hydroxide is 20%~60%, and isopropanol is 1 with the volume ratio of deionized water：4.
7. the new method for preparing silicon micro-nano hierarchy according to claim 1, it is characterised in that：In step S3,
The spot corrosion response time is 5~30min, and halogen ion concentration is 0.1mol/L~2mol/L.
8. according to the arbitrary described new method for preparing silicon micro-nano hierarchy of claim 1-7, it is characterised in that：Silver nanoparticle is thin
The thickness of film is 30~100nm.
9. according to the arbitrary described new method for preparing silicon micro-nano hierarchy of claim 1-7, it is characterised in that：The step
In S1, etch period is 20~60min.
10. according to the arbitrary described new method for preparing silicon micro-nano hierarchy of claim 1-7, it is characterised in that：The step
In rapid S4, etch period is 3~40min.
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