CN103194740A - Preparation method of metal silver ordered porous array membrane - Google Patents
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- CN103194740A CN103194740A CN2012100141068A CN201210014106A CN103194740A CN 103194740 A CN103194740 A CN 103194740A CN 2012100141068 A CN2012100141068 A CN 2012100141068A CN 201210014106 A CN201210014106 A CN 201210014106A CN 103194740 A CN103194740 A CN 103194740A
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Abstract
The invention discloses a preparation method of a metal silver ordered porous array membrane. The preparation method comprises the following steps of coating a polystyrene ball solution on a substrate, carrying out plasma etching to obtain a substrate coated with an incompact ordered polystyrene ball template, mixing silver nitrate, hydrofluoric acid and water to obtain a nucleation solution, putting the substrate coated with the incompact ordered polystyrene ball template into the nucleation solution, carrying out horizontal standing sedimentation to obtain silver seed crystal nuclei growing between the polystyrene balls on the substrate, orderly adding ammonia water, acetic acid, hydrazine hydrate and water into the silver nitrate aqueous solution to obtain a growth solution, putting the substrate with the silver seed crystal nuclei growing between the polystyrene balls into the growth solution, carrying out horizontal standing sedimentation to obtain an intermediate product, and putting the intermediate product into a solvent so that the polystyrene balls are dissolved in the solvent and the metal silver ordered porous array membrane is obtained. The preparation method has the characteristics of low cost, simple process and high target product quality.
Description
Technical field
The present invention relates to a kind of preparation method of array film, especially a kind of preparation method of argent ordered porous array film.
Background technology
Argent ordered porous array film has important application prospects in fields such as catalysis, surface enhanced Raman scatterings, also it can be used for silicon materials are carried out wet etching to obtain the ordered silicon nano-wires array.In the recent period, people are in order to obtain argent ordered porous array film, made unremitting effort, as " a kind of method and the electric deposition device for preparing metallic submicron microsphere array film " that discloses among the Chinese invention patent application documents CN 101844743A that announces on September 29th, 2010.The method of mentioning in this application file is, earlier the method for polystyrene microsphere by vertical self-assembly obtained to be grown in the ordered microsphere array film on the conductive glass, and with it as starting template, adopt sol-gel method synthetic silica large hole nano net and be used as the second step template, the method for recycling electrochemical deposition obtains being attached to the metallic submicron microsphere array film on the conductive glass.Yet, though this preparation method has obtained the argent submicron microsphere array film, exist weak point also, at first, the quality of final product is difficult to guarantee, its cause is, the one, by the substrate surface modification handle make polystyrene microsphere and substrate bonding force a little less than, when causing it to put into solution, polystyrene microsphere is easy to come off, cause the defective of template to increase, the 2nd, in the forming process of second template (anti-albuminous membranae), use colloidal solution, because the viscous modulus of colloidal solution itself is bigger, if polystyrene microsphere film too thick (being that the microballoon number of plies is too much), then the hole between the deep layer place microballoon can not be completely filled, and can form a lot of defectives; Secondly, preparation technology is numerous and diverse, not only time-consuming, but also power consumption, and self-assembly process wherein needed more than 4 days, and high-temperature calcination was just formed silicon-dioxide counter opal structure and removal polystyrene microsphere in 5 hours; Again, the substrate of use not only needs good electrical conductivity, also needs it is reached 12 hours surface modification; At last, need to use electrodeposition apparatus to carry out galvanic deposit, strengthened the cost of preparation.
Summary of the invention
The technical problem to be solved in the present invention provides the preparation method of the argent ordered porous array film that a kind of process is simple, cost is low for overcoming weak point of the prior art.
For solving technical problem of the present invention, the technical scheme that adopts is: the preparation method of argent ordered porous array film comprises template, and particularly completing steps is as follows:
Step 1, the spherical diameter that with concentration is 2.3～2.7wt% earlier is that the polystyrene spheres solution of 500～2000nm is applied on the substrate, again the substrate that is equipped with polystyrene spheres on it is placed the plasma clean machine to use plasma etching 3min at least, obtain being equipped with on it substrate of the polystyrene ball template of loose shape ordered arrangement;
Step 2, the hydrofluoric acid and the water that with Silver Nitrate, concentration are 38～42wt% earlier are 0.83～0.87 according to weight ratio: stir after 5: 992.15～996.15 the mixed, obtain nucleation solution, again the substrate that is equipped with the polystyrene ball template of loose shape ordered arrangement on it is placed nucleation solution level under 25～29 ℃ to leave standstill and deposit 80s at least, obtain that growth has silver-colored seed crystal nuclear between the on-chip polystyrene spheres;
Step 3, be that 0.49～0.53: 100 ratio is dissolved in Silver Nitrate in the water according to weight ratio earlier, obtain silver nitrate aqueous solution, the ammoniacal liquor, Glacial acetic acid, the concentration that add concentration more successively in the silver nitrate aqueous solution and be 25～29wt% are hydrazine hydrate and the water of 78～82wt%, obtain growth solution, wherein, the weight ratio between the Silver Nitrate in the growth solution, ammoniacal liquor, Glacial acetic acid, hydrazine hydrate and the water is 0.49～0.53: 152.1～152.5: 33.4～33.8: 6.23～6.27: 716.30～716.34;
Step 4, the substrate that elder generation has silver-colored seed crystal to examine growth between the polystyrene spheres that is equipped with on it places the growth solution level under 25～29 ℃ to leave standstill and deposits 4.5min at least, obtain intermediate product, intermediate product is placed the molten polystyrene spheres that goes of solvent, making thickness is that 150～250nm, bore dia are 100～1800nm, hole cycle to be the argent ordered porous array film of 500～2000nm again.
As the preparation method's of argent ordered porous array film further improvement, described substrate is silicon chip, or sheet glass, or ceramic plate; Described before polystyrene spheres solution is applied on the substrate, use acetone successively, the mixed solution of ammoniacal liquor, hydrogen peroxide and deionized water, and deionized water ultrasonic cleaning substrate earlier; The mixed solution of described ammoniacal liquor, hydrogen peroxide and deionized water is the ammoniacal liquor of 25～28wt%, hydrogen peroxide that concentration is 28～32wt% and deionized water according to volume ratio by concentration is that 1: 1: 5 ratio is formulated; Described coating is spin coating, or drips and to be coated with, or lifts; The described plasma body of the on-chip polystyrene spheres of plasma etching that uses is argon plasma, and the power of etching is 18W, and the time of etching is 3～45min; The purity of described Glacial acetic acid is the AR level; The described molten solvent that removes polystyrene spheres is methylene dichloride or toluene, time to be at least 5min.
Beneficial effect with respect to prior art is, one, use scanning electron microscope and X-ray diffractometer to characterize respectively to the target product that makes, by its result as can be known, target product is that to be overlying on on-chip thickness be that 150～250nm, bore dia are 100～1800nm, hole cycle to be the ordered porous array film of 500～2000nm.This ordered porous array film is made of argent.They are two years old, preparation method's cost is low, simple, efficient: the one, use the plasma etching polystyrene spheres in the preparation process, both reduce sphere diameter and increased the ball distance, also make the fusion adhesion that produces between (during the multilayer) and ball and substrate between the ball slightly, make mutual adhesive power stronger, stopped to be placed on polystyrene spheres caducous phenomenon in back in nucleation and the growth solution; Nucleation and growth solution are inorganic salt solution in addition, and its viscous modulus is very little, even the number of plies of ball is too much, to the influence of metal deposition effect also very little; Have laid a good foundation for making high-quality target product.Two are to use coating technology to make the polystyrene ball template only needs about 5 minutes, and moltenly goes the polystyrene spheres in the intermediate product not only not need high-temperature calcination, also only needs get final product in 5 minutes.The 3rd, substrate except no electroconductibility requires, is not also needed it is carried out surface Modification.The 4th, need not carry out galvanic deposit, the investment of having saved equipment has reduced the cost for preparing.
As the further embodiment of beneficial effect, the one, substrate is preferably silicon chip, or sheet glass, or ceramic plate, except the alternative leeway of substrate is big, also is convenient to implement.The 2nd, before polystyrene spheres solution is applied on the substrate, the preferred acetone that uses successively earlier, the mixed solution of ammoniacal liquor, hydrogen peroxide and deionized water, and deionized water ultrasonic cleaning substrate, wherein, the mixed solution of ammoniacal liquor, hydrogen peroxide and deionized water is the ammoniacal liquor of 25～28wt%, hydrogen peroxide that concentration is 28～32wt% and deionized water according to volume ratio by concentration preferably is that 1: 1: 5 ratio is formulated, is beneficial to the coating of polystyrene spheres solution.The 3rd, coating is preferably spin coating, or drips and be coated with, or lifts, and all is convenient to effectively polystyrene spheres solution is applied on the substrate.Four are to use the plasma body of the on-chip polystyrene spheres of plasma etching to be preferably argon plasma, and the power of etching is preferably 18W, and the time of etching is preferably 3～45min, are beneficial to the polystyrene spheres that obtains desired size.The 5th, the purity of Glacial acetic acid is preferably the AR level, has avoided the introducing of impurity, has guaranteed the quality of growth solution.The 6th, the molten solvent that removes polystyrene spheres is preferably methylene dichloride or toluene, time and preferably is at least 5min, has guaranteed to dissolve away fully in the limited time polystyrene spheres.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that scanning electron microscope (SEM) characterizes to a plurality of target products that make and intermediate product.Demonstrated to this SEM clear picture the whole pattern of target product and intermediate product; Wherein, Fig. 1 a, Fig. 1 b and Fig. 1 c are the target product of the ordered porous array formation for preparing under the individual layer polystyrene ball template, Fig. 1 a and Fig. 1 b are the target product of the polystyrene spheres preparation of 500nm for using spherical diameter, its bore dia is respectively 230nm and 150nm, Fig. 1 c is the target product of the polystyrene spheres preparation of 2 μ m for using spherical diameter, and its bore dia is 1.3 μ m; Fig. 1 d is the intermediate product that the ordered porous array for preparing under the double-deck polystyrene ball template constitutes, and it is the intermediate product of the polystyrene spheres preparation of 2 μ m for using spherical diameter, and its bore dia is 1 μ m, and the illustration in the lower right corner is its local enlarged view among the figure.
Fig. 2 uses one of result that X-ray diffraction (XRD) instrument characterizes to target product shown in Figure 1 and intermediate product.XRD spectra shows that target product is made of argent, and intermediate product contains argent.
Embodiment
At first buy from market or make with ordinary method:
Spherical diameter is the polystyrene spheres solution of 500～2000nm; Silver Nitrate; Hydrofluoric acid; Water; Ammoniacal liquor; Glacial acetic acid; Hydrazine hydrate; Silicon chip, sheet glass and ceramic plate as substrate; As molten methylene dichloride and the toluene that removes the solvent of polystyrene spheres.
Earlier use acetone successively, the mixed solution of ammoniacal liquor, hydrogen peroxide and deionized water, and deionized water ultrasonic cleaning substrate; Wherein, the mixed solution of ammoniacal liquor, hydrogen peroxide and deionized water be the ammoniacal liquor of 25～28wt%, hydrogen peroxide that concentration is 28～32wt% and deionized water according to volume ratio by concentration is that 1: 1: 5 ratio is formulated.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, the spherical diameter that with concentration is 2.3wt% earlier are that the polystyrene spheres solution of 500nm is applied on the substrate; Wherein, substrate is silicon chip, applies to be spin coating.Again the substrate that is equipped with polystyrene spheres on it is placed the plasma clean machine to use argon plasma etch 3min; Wherein, the power of etching is 18W, obtains being equipped with on it substrate of the polystyrene ball template of loose shape ordered arrangement.
Step 2 earlier is to stir after the hydrofluoric acid of 38wt% and the mixed that water is 0.83: 5: 992.15 Silver Nitrate, concentration according to weight ratio, obtains nucleation solution.The substrate that is equipped with the polystyrene ball template of loose shape ordered arrangement on it is placed the nucleation solution level under 25 ℃ to leave standstill deposition 100s, obtaining growing between the on-chip polystyrene spheres has silver-colored seed crystal nuclear again.
Step 3 is that 0.49: 100 ratio is dissolved in Silver Nitrate in the water according to weight ratio earlier, obtains silver nitrate aqueous solution.The ammoniacal liquor, Glacial acetic acid, the concentration that add concentration more successively in the silver nitrate aqueous solution and be 25wt% are hydrazine hydrate and the water of 78wt%, obtain growth solution; Wherein, the weight ratio between the Silver Nitrate in the growth solution, ammoniacal liquor, Glacial acetic acid, hydrazine hydrate and the water is 0.49: 152.5: 33.4: 6.27: 716.30, the purity of Glacial acetic acid was the AR level.
Step 4 has growth between the polystyrene spheres that is equipped with on it substrate of silver-colored seed crystal nuclear to place the growth solution level under 25 ℃ to leave standstill deposition 6min earlier, obtains intermediate product.Again intermediate product is placed the molten polystyrene spheres that goes wherein of solvent; It is wherein, molten that to remove the solvent of polystyrene spheres be that methylene dichloride, time are 5min.Make as shown in Figure 1a, and the argent ordered porous array film shown in the XRD spectral line among Fig. 2.
Embodiment 2
The concrete steps of preparation are:
Step 1, the spherical diameter that with concentration is 2.4wt% earlier are that the polystyrene spheres solution of 500nm is applied on the substrate; Wherein, substrate is silicon chip, applies to be spin coating.Again the substrate that is equipped with polystyrene spheres on it is placed the plasma clean machine to use argon plasma etch 7min; Wherein, the power of etching is 18W, obtains being equipped with on it substrate of the polystyrene ball template of loose shape ordered arrangement.
Step 2 earlier is to stir after the hydrofluoric acid of 39wt% and the mixed that water is 0.84: 5: 993.15 Silver Nitrate, concentration according to weight ratio, obtains nucleation solution.The substrate that is equipped with the polystyrene ball template of loose shape ordered arrangement on it is placed the nucleation solution level under 26 ℃ to leave standstill deposition 95s, obtaining growing between the on-chip polystyrene spheres has silver-colored seed crystal nuclear again.
Step 3 is that 0.5: 100 ratio is dissolved in Silver Nitrate in the water according to weight ratio earlier, obtains silver nitrate aqueous solution.The ammoniacal liquor, Glacial acetic acid, the concentration that add concentration more successively in the silver nitrate aqueous solution and be 26wt% are hydrazine hydrate and the water of 79wt%, obtain growth solution; Wherein, the weight ratio between the Silver Nitrate in the growth solution, ammoniacal liquor, Glacial acetic acid, hydrazine hydrate and the water is 0.5: 152.4: 33.5: 6.26: 716.31, the purity of Glacial acetic acid was the AR level.
Step 4 has growth between the polystyrene spheres that is equipped with on it substrate of silver-colored seed crystal nuclear to place the growth solution level under 26 ℃ to leave standstill deposition 5.7min earlier, obtains intermediate product.Again intermediate product is placed the molten polystyrene spheres that goes wherein of solvent; It is wherein, molten that to remove the solvent of polystyrene spheres be that methylene dichloride, time are 6min.Make shown in Fig. 1 b, and the argent ordered porous array film shown in the XRD spectral line among Fig. 2.
Embodiment 3
The concrete steps of preparation are:
Step 1, the spherical diameter that with concentration is 2.5wt% earlier are that the polystyrene spheres solution of 1300nm is applied on the substrate; Wherein, substrate is silicon chip, applies to be spin coating.Again the substrate that is equipped with polystyrene spheres on it is placed the plasma clean machine to use argon plasma etch 23min; Wherein, the power of etching is 18W, obtains being equipped with on it substrate of the polystyrene ball template of loose shape ordered arrangement.
Step 2 earlier is to stir after the hydrofluoric acid of 40wt% and the mixed that water is 0.85: 5: 994.15 Silver Nitrate, concentration according to weight ratio, obtains nucleation solution.The substrate that is equipped with the polystyrene ball template of loose shape ordered arrangement on it is placed the nucleation solution level under 27 ℃ to leave standstill deposition 90s, obtaining growing between the on-chip polystyrene spheres has silver-colored seed crystal nuclear again.
Step 3 is that 0.51: 100 ratio is dissolved in Silver Nitrate in the water according to weight ratio earlier, obtains silver nitrate aqueous solution.The ammoniacal liquor, Glacial acetic acid, the concentration that add concentration more successively in the silver nitrate aqueous solution and be 27wt% are hydrazine hydrate and the water of 80wt%, obtain growth solution; Wherein, the weight ratio between the Silver Nitrate in the growth solution, ammoniacal liquor, Glacial acetic acid, hydrazine hydrate and the water is 0.51: 152.3: 33.6: 6.25: 716.32, the purity of Glacial acetic acid was the AR level.
Step 4 has growth between the polystyrene spheres that is equipped with on it substrate of silver-colored seed crystal nuclear to place the growth solution level under 27 ℃ to leave standstill deposition 5.3min earlier, obtains intermediate product.Again intermediate product is placed the molten polystyrene spheres that goes wherein of solvent; It is wherein, molten that to remove the solvent of polystyrene spheres be that methylene dichloride, time are 7min.Make and be similar to shown in Fig. 1 c, and the argent ordered porous array film shown in the XRD spectral line among Fig. 2.
Embodiment 4
The concrete steps of preparation are:
Step 1, the spherical diameter that with concentration is 2.6wt% earlier are that the polystyrene spheres solution of 2000nm is applied on the substrate; Wherein, substrate is silicon chip, applies to be spin coating.Again the substrate that is equipped with polystyrene spheres on it is placed the plasma clean machine to use argon plasma etch 31min; Wherein, the power of etching is 18W, obtains being equipped with on it substrate of the polystyrene ball template of loose shape ordered arrangement.
Step 2 earlier is to stir after the hydrofluoric acid of 41wt% and the mixed that water is 0.86: 5: 995.15 Silver Nitrate, concentration according to weight ratio, obtains nucleation solution.The substrate that is equipped with the polystyrene ball template of loose shape ordered arrangement on it is placed the nucleation solution level under 28 ℃ to leave standstill deposition 85s, obtaining growing between the on-chip polystyrene spheres has silver-colored seed crystal nuclear again.
Step 3 is that 0.52: 100 ratio is dissolved in Silver Nitrate in the water according to weight ratio earlier, obtains silver nitrate aqueous solution.The ammoniacal liquor, Glacial acetic acid, the concentration that add concentration more successively in the silver nitrate aqueous solution and be 28wt% are hydrazine hydrate and the water of 81wt%, obtain growth solution; Wherein, the weight ratio between the Silver Nitrate in the growth solution, ammoniacal liquor, Glacial acetic acid, hydrazine hydrate and the water is 0.52: 152.2: 33.7: 6.24: 716.33, the purity of Glacial acetic acid was the AR level.
Step 4 has growth between the polystyrene spheres that is equipped with on it substrate of silver-colored seed crystal nuclear to place the growth solution level under 28 ℃ to leave standstill deposition 4.9min earlier, obtains intermediate product.Again intermediate product is placed the molten polystyrene spheres that goes wherein of solvent; It is wherein, molten that to remove the solvent of polystyrene spheres be that methylene dichloride, time are 8min.Make shown in Fig. 1 c, and the argent ordered porous array film shown in the XRD spectral line among Fig. 2.
Embodiment 5
The concrete steps of preparation are:
Step 1, the spherical diameter that with concentration is 2.7wt% earlier are that the polystyrene spheres solution of 2000nm is applied on the substrate; Wherein, substrate is silicon chip, applies to be spin coating.Again the substrate that is equipped with polystyrene spheres on it is placed the plasma clean machine to use argon plasma etch 45min; Wherein, the power of etching is 18W, obtains being equipped with on it substrate of the polystyrene ball template of loose shape ordered arrangement.
Step 2 earlier is to stir after the hydrofluoric acid of 42wt% and the mixed that water is 0.87: 5: 996.15 Silver Nitrate, concentration according to weight ratio, obtains nucleation solution.The substrate that is equipped with the polystyrene ball template of loose shape ordered arrangement on it is placed the nucleation solution level under 29 ℃ to leave standstill deposition 80s, obtaining growing between the on-chip polystyrene spheres has silver-colored seed crystal nuclear again.
Step 3 is that 0.53: 100 ratio is dissolved in Silver Nitrate in the water according to weight ratio earlier, obtains silver nitrate aqueous solution.The ammoniacal liquor, Glacial acetic acid, the concentration that add concentration more successively in the silver nitrate aqueous solution and be 29wt% are hydrazine hydrate and the water of 82wt%, obtain growth solution; Wherein, the weight ratio between the Silver Nitrate in the growth solution, ammoniacal liquor, Glacial acetic acid, hydrazine hydrate and the water is 0.53: 152.1: 33.8: 6.23: 716.34, the purity of Glacial acetic acid was the AR level.
Step 4 has growth between the polystyrene spheres that is equipped with on it substrate of silver-colored seed crystal nuclear to place the growth solution level under 29 ℃ to leave standstill deposition 4.5min earlier, obtains shown in Fig. 1 d, and the intermediate product shown in the XRD spectral line among Fig. 2.
Select silicon chip or sheet glass or ceramic plate as substrate more respectively for use, apply to spin coating or drip and be coated with or lift, as molten methylene dichloride or the toluene that removes the solvent of polystyrene spheres, repeat above-described embodiment 1～5, made equally as or be similar to shown in Figure 1, and the argent ordered porous array film shown in the XRD spectral line among Fig. 2.
Obviously, those skilled in the art can carry out various changes and modification to the preparation method of argent ordered porous array film of the present invention and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (8)
1. the preparation method of an argent ordered porous array film comprises template, it is characterized in that completing steps is as follows:
Step 1, the spherical diameter that with concentration is 2.3～2.7wt% earlier is that the polystyrene spheres solution of 500～2000nm is applied on the substrate, again the substrate that is equipped with polystyrene spheres on it is placed the plasma clean machine to use plasma etching 3min at least, obtain being equipped with on it substrate of the polystyrene ball template of loose shape ordered arrangement;
Step 2, the hydrofluoric acid and the water that with Silver Nitrate, concentration are 38～42wt% earlier are 0.83～0.87 according to weight ratio: stir after 5: 992.15～996.15 the mixed, obtain nucleation solution, again the substrate that is equipped with the polystyrene ball template of loose shape ordered arrangement on it is placed nucleation solution level under 25～29 ℃ to leave standstill and deposit 80s at least, obtain that growth has silver-colored seed crystal nuclear between the on-chip polystyrene spheres;
Step 3, be that 0.49～0.53: 100 ratio is dissolved in Silver Nitrate in the water according to weight ratio earlier, obtain silver nitrate aqueous solution, the ammoniacal liquor, Glacial acetic acid, the concentration that add concentration more successively in the silver nitrate aqueous solution and be 25～29wt% are hydrazine hydrate and the water of 78～82wt%, obtain growth solution, wherein, the weight ratio between the Silver Nitrate in the growth solution, ammoniacal liquor, Glacial acetic acid, hydrazine hydrate and the water is 0.49～0.53: 152.1～152.5: 33.4～33.8: 6.23～6.27: 716.30～716.34;
Step 4, the substrate that elder generation has silver-colored seed crystal to examine growth between the polystyrene spheres that is equipped with on it places the growth solution level under 25～29 ℃ to leave standstill and deposits 4.5min at least, obtain intermediate product, intermediate product is placed the molten polystyrene spheres that goes of solvent, making thickness is that 150～250nm, bore dia are 100～1800nm, hole cycle to be the argent ordered porous array film of 500～2000nm again.
2. the preparation method of argent ordered porous array film according to claim 1 is characterized in that substrate is silicon chip, or sheet glass, or ceramic plate.
3. the preparation method of argent ordered porous array film according to claim 2, it is characterized in that before polystyrene spheres solution is applied on the substrate, earlier use acetone successively, the mixed solution of ammoniacal liquor, hydrogen peroxide and deionized water, and deionized water ultrasonic cleaning substrate.
4. the preparation method of argent ordered porous array film according to claim 3, the mixed solution that it is characterized in that ammoniacal liquor, hydrogen peroxide and deionized water is the ammoniacal liquor of 25～28wt%, hydrogen peroxide that concentration is 28～32wt% and deionized water according to volume ratio by concentration is that 1: 1: 5 ratio is formulated.
5. the preparation method of argent ordered porous array film according to claim 1 is characterized in that coating is spin coating, or drips and be coated with, or lifts.
6. the preparation method of argent ordered porous array film according to claim 1 is characterized in that using the plasma body of the on-chip polystyrene spheres of plasma etching to be argon plasma, and the power of etching is 18W, and the time of etching is 3～45min.
7. the preparation method of argent ordered porous array film according to claim 1, the purity that it is characterized in that Glacial acetic acid is the AR level.
8. the preparation method of argent ordered porous array film according to claim 1 is characterized in that the molten solvent that removes polystyrene spheres is methylene dichloride or toluene, time to be at least 5min.
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| CN103950889A (en) * | 2014-05-08 | 2014-07-30 | 清华大学 | Preparation method of silicon nanowire array with excellent field emission performance and tip structure |
| CN106770157A (en) * | 2016-11-23 | 2017-05-31 | 国家纳米科学中心 | A kind of surface enhanced Raman substrate and preparation method thereof |
| CN107101988A (en) * | 2017-03-16 | 2017-08-29 | 中国科学院合肥物质科学研究院 | A kind of high density nanometer pinpoint array of golden film covering and its application |
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| CN107101988B (en) * | 2017-03-16 | 2020-08-28 | 中国科学院合肥物质科学研究院 | Gold film covered high-density nanometer needle tip array and application thereof |
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