CN101074486A - Method for producing nanostructure - Google Patents

Abstract

The present invention provides a method for producing nanostructure where a structure having dents with regular arrangement can be obtained in a short time without using substances such as chromic acid unpreferable to the environment. The mentioned method includes: a peeling stage where electrolysis is performed with an aluminum member comprising an aluminum substrate and an anode oxide film present on the surface of the aluminum substrate as the cathode, thus the anode oxide film and the aluminum substrate are peeled, so as to obtain a structure composed of the anode oxide film, and, in the peeling stage, the electrolysis is performed in such a manner that electric current is made to flow through the surface of the anode oxide film.

Description

The manufacture method of nanostructure

Technical field

The present invention relates to nanostructure and manufacture method thereof.

Background technology

In technical fields such as metal and semi-conductive film, fine rule, point, known when the time than the little size of a certain characteristic length, by the motion of sealing unbound electron, electric, light and unique phenomenon chemistry just can appear.This phenomenon is known as " quantum-mechanical size effect (quantum size effect) ".Now, the research and development of using the functional materials of this unique phenomenon prevail.Specifically, the material with structure also finer than hundreds of nm is known as " nanostructure " or " microstructure ", becomes one of object of developing material.

As the manufacture method of this microstructure, for example, can enumerate the method for directly making nanostructure by the semiconductor processing technology that comes from Micropicture formation technology such as photoetching, electron rays exposure, X ray exposure.

Wherein, caused people's attention about the research of the manufacture method of the nanostructure of microtexture, and carried out a lot with rule.

For example, as the method that forms the rule structure made from own specification, can be set forth in the electrolytic solution aluminium is implemented the anodic alumina films (anodic oxidation coating) that anodic oxidation treatment obtains.Known in anodic oxidation coating, formed a plurality of minute apertures (micropore) that have about hundreds of nm to hundreds of nm left and right sides diameter regularly.The known regularization that utilizes this anodic oxidation coating oneself, when obtaining complete rule and arranging, theoretically, being formed centrally the bottom surface in micropore being is the hexagonal column unit of regular hexagon, the line that connects adjacent micropore is formed equilateral triangle.

For example, in non-patent literature 1, record the micropore size deviation in the anodic oxidation coating below 3%.In addition, in non-patent literature 2, put down in writing in anodic oxidation coating, be accompanied by the carrying out of oxidation, formed the situation of micropore naturally.In addition, in non-patent literature 3, proposed with the porous anode tunicle, on the Si substrate, formed the situation of Au lattice array as mask.

Maximum feature as the material of anodic oxidation coating is, is chosen in the honeycomb structure that uniformly-spaced forms a plurality of micropores with respect to substrate surface almost on the vertical direction, basically abreast.In addition, can more freely control aperture, span and hole depth this point also is the feature (referring to non-patent literature 3) that other material does not possess.

As the applicating example of anodic oxidation coating, known have various type of device such as nano-device, magnetic device, twinkler.For example, in patent documentation 1, put down in writing as magnetic device and in micropore, filled magneticmetal Co, Ni, in micropore, filled ZnO, the application examples of the enzyme/antibody of in micropore, filling as biosensor as luminescent material.

Further, in field of biosensors, in patent documentation 2, put down in writing and used the example of using sample table at the structure of the micropore inside of anodic oxidation coating filler metal as Raman's spectrum analysis.

Raman scattering is an incident light (photon) when shining particle scattering, causes the non-resilient collision with particle, and makes the scattering of energy variation.Though Raman scattered light uses as the spectrum analysis method, for sensitivity and the precision that improves analysis, the scattered intensity that is used in mensuration strengthens and just becomes a problem.

As the phenomenon that strengthens Raman scattered light, known have face to strengthen resonant Raman scattering (SERRS:Surface-Enhanced Resonance Raman Scattering) phenomenon.This phenomenon enhanced phenomenon that is the scattering that makes certain molecule that absorbs on surfaces such as metal electrode, colloidal sol, crystallization, evaporating film, semi-conductor in the solution especially, in gold or silver, can be seen 1011～1014 times remarkable enhanced effect.Though the genesis mechanism of SERRS phenomenon is now also indeterminate, can think that the resonance of aftermentioned face plasma unit exerts an influence.In patent documentation 2,, be purpose with the principle of utilizing the resonance of plasma unit as the means that strengthen Raman scattering intensity.

The resonance of plasma unit is that the metallic surface becomes excited state in the surface irradiation light time to precious metals such as gold and silver, causes that plasman ripple and the hertzian wave as the local electronic density wave interacts (resonance excitation), forms the phenomenon of resonance state.Wherein, face plasma unit's resonance (SPR:SurfacePlasmon Resonance) is that the unbound electron of metallic surface becomes the state of having encouraged to the metallic surface irradiates light time, and unbound electron collectively vibrates, generation face plasma unit resonance wave, thus the phenomenon of strong electric field produced.

The near zone on the surface that the resonance of plasma unit takes place, particularly from surperficial 200nm with the zone about interior, find to reach several doubly (in the example, 10 ⁸～10 ¹⁰Electric field doubly) strengthens, and observes various optical effects and significantly improves.For example, when light incided on the prism that has evaporated golden film such as grade with the angle more than the critical angle, the change in dielectric constant of film surface changed as the intensity of reflected light that causes because of face plasma unit resonance effect, can be detected in high sensitivity.

Specifically, when using the SPR device of application surface plasma unit resonance effect, can carry out reacting weight and the mensuration of binding capacity and the analysis of rate theory between biomolecules unmarked and in real time.The SPR device is applied to the research of various material interphase interactions such as immune response, signal transmission, protein, nucleic acid, recently, has also delivered the paper (with reference to non-patent literature 4) that utilizes SPR device analysis trace dioxin (dioxin).

As the method that increases the resonance of plasma unit, examined the whole bag of tricks, knownly make metal not become film and become isolated particle, make the method for plasma unit localization thus.For example, in above-mentioned patent documentation 2, put down in writing and on the pore of the anodic oxidation coating of regularization, metallics is set and carries out method of localization.

At this, under the situation of utilizing local plasma unit resonance,,, realizes the research report of the first state that resonates of easier generation plasma because the gap between the metallics strengthens strength of electric field if having when existing near metallics by metallics.(referring to non-patent literature 5).

Utilize the self-lawization of anodic oxidation coating, in the method for the anodic oxidation coating of the arrangement of manufacturing micropore rule, originally, under specific electrolytic condition, carry out electrolysis for a long time, carry out after the regularization operation of carrying out the micropore generation regularly, near the bottom of exposing the micropore of permutation the most regularly on the surface, carry out in the mixed aqueous solution of chromic acid and phosphoric acid, being dissolved in the demoulding operation that obtains anodic oxidation coating in the regularization operation usually.

In addition, in patent documentation 3, put down in writing and aluminium parts or its alloy are applied anodic oxidation treatment form porous layer, use contrary electrolytic process to peel off this porous layer only, obtain the method for porous layer from fertile material.

In non-patent literature 6, put down in writing to make and used after the attenuation of blocking layer contrary electrolysis process to peel off the method for anodic oxidation coating from aluminium parts by the electric current restoring method.

Patent documentation 1 spy opens the 2000-31462 communique

Patent documentation 2 spies open the 2003-268592 communique

Patent documentation 3 spies open clear 61-88495 communique

Non-patent literature 1 H.Masuda et.Al., Jpn.J.Appl.Phys., Vol.37 (1998), pp.L1340-1342, Part2, No.11A, 1 November 1998 (Fig. 2)

Non-patent literature 2 " sufacing brief guide ", (1998) are compiled by (society) sufacing association, Nikkan Kogyo Shimbun, p.490-553

Non-patent literature 3 beneficial Tian Xiushu, " based on the high regular metal nano hole path of anodised aluminium ", solid-state physics, 1996, the 31st volume, No. 5, p.493-499

Non-patent literature 4 light portions etc., ANALYTICA CHIMICA ACTA 201,434:2:223-230

This swells it non-patent literature 5 Gang, " metal nanoparticle interacts and relates to the investigation of biosensor ", [on line], [putting down into retrieval on November 27th, 15], Internet＜URL:http: //www.plasmon.jp/reports/okamoto.pdf 〉

Non-patent literature 6 aluminium Yan Jiu Hui Chi, 1985, No.7, No. 201, logical volume, p.7～8

But, because the thickness difference of anodic oxidation coating, so use the demoulding operation of chromic acid and phosphoric acid mixing solutions need carry out several hours to tens hours long-time usually.In addition, because the anodic oxidation coating dissolving just can not effectively utilize.Further, in the such environment of chromic acid, need to use not preferred material.

In addition, should be understood that, can use electric current restoring method by record in patent documentation 3 and the non-patent literature 6, make and use after the thickness attenuation of tunicle contrary electrolysis process when aluminium parts is peeled off the method for anodic oxidation coating, make the bottom of micropore become the fine hole of branch branching by the electric current restoring method, the pit of peeling off the aluminium parts surface rule arrangement that obtains will be chaotic.Therefore, should be understood that, for example,, can not use with on the sample table etc. at Raman's spectrum analysis even form anodic oxidation coating obtaining further applying on the aluminium parts anodic oxidation treatment.

Summary of the invention

Therefore, the objective of the invention is to, a kind of manufacture method of structure and the structure that obtains by this method are provided, in the environment of chromic acid etc., do not use not preferred material, at short notice, can access structure with pit that rule arranges.

The result that the inventor studies assiduously to achieve these goals, the aluminium parts of discovery by will having anodic oxidation coating is as negative electrode, electrolysis is implemented so that electric current flows through in surface to anodic oxidation coating only, just can be at short notice, obtain having the structure of the pit that rule arranges, thereby finished the present invention.

That is, the invention provides following (1)～(11).

(1) a kind of manufacture method of structure, comprise: the aluminium parts by the anodic oxidation coating that will have aluminium base and exist on above-mentioned aluminium base surface is implemented electrolysis as negative electrode makes above-mentioned anodic oxidation coating and above-mentioned aluminium base peel off, obtain the stripping process of the structure that is made of anodic oxidation coating, wherein

In above-mentioned stripping process, implement above-mentioned electrolysis according to the mode that makes electric current flow through the surface of above-mentioned anodic oxidation coating.

(2) manufacture method of the structure described in above-mentioned (1) wherein in above-mentioned stripping process, is implemented above-mentioned electrolysis according to the mode that makes electric current only flow through the surface of above-mentioned anodic oxidation coating.

(3) manufacture method of the structure described in above-mentioned (2), wherein, in above-mentioned stripping process, make electrolytic solution contact the surface of above-mentioned anodic oxidation coating, simultaneously electrolytic solution contacted under the state of the side of above-mentioned anodic oxidation coating and above-mentioned aluminium base to implement above-mentioned electrolysis.

(4) manufacture method of any described structure in above-mentioned (1)～(3) in above-mentioned stripping process, becomes 0.1A/dm at current value ²After the following time point, finish above-mentioned electrolysis.。

(5) a kind of structure that manufacture method obtained by any described structure in above-mentioned (1)～(4).

(6) a kind of manufacture method of structure, comprise: implement electrolysis by the aluminium parts of the anodic oxidation coating that will have aluminium base and on above-mentioned aluminium base surface, exist as negative electrode above-mentioned anodic oxidation coating and above-mentioned aluminium base are peeled off, obtain the stripping process of the structure that constitutes by aluminium base with a plurality of pits;

Aluminium base with above-mentioned a plurality of pits is implemented anodic oxidation treatment, obtain the anodic oxidation treatment operation of the structure that constitutes by the aluminium base that has the anodic oxidation coating that has micropore on the surface; Wherein,

In above-mentioned stripping process, implement above-mentioned electrolysis according to the mode that makes electric current flow through the surface of above-mentioned anodic oxidation coating.

(7) manufacture method of the structure described in above-mentioned (6) in above-mentioned stripping process, is implemented above-mentioned electrolysis according to the mode that makes electric current only flow through the surface of above-mentioned anodic oxidation coating.

(8) manufacture method of the structure described in above-mentioned (7), in above-mentioned stripping process, make electrolytic solution contact the surface of above-mentioned anodic oxidation coating, simultaneously electrolytic solution contacted under the state of the side of above-mentioned anodic oxidation coating and above-mentioned aluminium base to implement above-mentioned stripping process.

(9) manufacture method of any described structure in above-mentioned (6)～(8) in above-mentioned stripping process, becomes 0.1A/dm at current value ²After the following time point, finish above-mentioned electrolysis.

(10) manufacture method of any described structure in above-mentioned (6)～(9), further comprise: after above-mentioned anodic oxidation treatment operation, the structure that is made of the aluminium base that has the anodic oxidation coating that has above-mentioned micropore on the surface is implemented the chemical dissolution treatment process that chemical dissolution is handled.

(11) a kind of structure that manufacture method obtained by any described structure in above-mentioned (6)～(10).

According to the manufacture method of structure of the present invention, just can be at short notice, obtain having the structure of the pit that rule arranges.

Description of drawings

Fig. 1 be expression will have aluminium base and anodic oxidation coating aluminium parts as negative electrode, the schematic chart that the timeliness that makes surface that electric current only flows through anodic oxidation coating implement the electric current under the electrolytic situation changes.

Fig. 2 is the explanatory view of structure manufacture method of the present invention.

Fig. 3 is the schematic explanatory view that is used for contrary electrolytic special fixtures.

Fig. 4 is the explanatory view of method that calculates the regularization degree in hole.

Nomenclature

1,2,4,5,7,8,16,32 micropores

3,6,9 circles, 10 aluminium parts

12,24,34 aluminium bases, 14,30 anodic oxidation coating

18 blocking layers, 20,28 structures

22,26 pits, 40 negative electrodes

42 encapsulation, 44 electrolyte stream inlet

The outlet of 46 electrolyte stream

Embodiment

Describe the present invention below in detail.

First form of the present invention is a kind of manufacture method of structure, comprise: make above-mentioned anodic oxidation coating and above-mentioned aluminium base peel off, obtain the stripping process of anodic oxidation coating by having aluminium base and implementing electrolysis as negative electrode at the aluminium parts of the surperficial anodic oxidation coating that exists of aluminium base, wherein, in above-mentioned stripping process, make electric current only flow through above-mentioned anodic oxidation coating surface, implement above-mentioned electrolysis.

＜aluminium parts 〉

The aluminium parts of Shi Yonging has aluminium base and is present in the lip-deep anodic oxidation coating of above-mentioned aluminium base in the present invention.Can be by aluminium base being shown implementing anodic oxidation treatment obtains this aluminium parts.

＜aluminium base 〉

Do not limit aluminium base especially, for example, can list commercially available aluminium base; On low-purity aluminium (for example twice-laid stuff), evaporated the substrate of raffinal; By methods such as evaporation, sputter in surface coverage such as silicon wafer, quartz, glass the substrate of raffinal; The stacked resin substrate of aluminium.

In aluminium base, on the surface that anodic oxidation coating is set by anodic oxidation treatment, preferred aluminium purity more than 99.5 quality %, more preferably more than 99.80 quality %, in addition, preferably less than 99.99 quality %, more preferably below 99.95 quality %.Aluminium purity is when 99.5 quality % are above, and it is fully regular that arrange in the hole, can make at an easy rate during less than 99.99 quality %.

Preferably the surface of aluminium base is implemented skimming treatment and polished finish in advance.

＜skimming treatment 〉

Use acid, alkali, organic solvent etc. to carry out skimming treatment, its objective is that dissolving, removal are attached to the organic composition (mainly being lubricant component) on surface etc.In skimming treatment, can use existing known grease-removing agent.

Specifically, for example, can use commercially available various grease-removing agents to carry out degreasing by the method for regulation.

In addition, also can be in the aqueous sulfuric acid of about 40～70 ℃ of aqueous sodium hydroxide solution, PH 1～4, the temperature of about 30～50 ℃ of pH 10～13, temperature etc., in the time that produces bubble slightly from the aluminium surface, the dipping aluminium base carries out degreasing.

As preferred skimming treatment, illustrate for example with acetone and clean after the aluminium base, the method for in the sulfuric acid of 50 ℃ of PH 4, temperature, soaking.According to this method, owing to can remove the grease on aluminium surface, can cause the dissolving of aluminium on the other hand hardly, so carry out preferred.

＜polished finish 〉

For the surface that makes aluminium base does not have concavo-convexly, improve homogeneity and the reproducibility handled by the sealing of hole of electrolytic process etc., and carry out polished finish.

In the present invention, polished finish is not particularly limited, can uses existing known method.For example, can enumerate the method for the commercially available various abrasives (for example diamond, aluminum oxide) of the Ginding process, the combination that utilize various commercially available abrasive cloths and the method for polishing wheel, the method for implementing electrolytic polishing, enforcement chemical grinding.These methods can suitably be used in combination.

The electrolytic polishing of enumerating and the method for chemical grinding for example have the whole bag of tricks of compiling (calendar year 2001), putting down in writing in p.164-165 in aluminium handbook (the 6th edition), (society) Japanese aluminium association.

As preferred polished finish, enumerated and from the coarse particle to the fine particle, changed employed abrasive in time, use abrasive to carry out finishing method, implement the method for electrolytic polishing then.In this case, the abrasive as final use is preferably #1500.According to this method, making under the situation of aluminium base through calendering, even can produce the calendering striped during calendering, the calendering striped is disappeared.

For example, by polished finish, can obtain average surface roughness Ra is that 0.03 μ m is following, the surface of glossiness more than 70%.Preferred surface roughness Ra is below the 0.02 μ m.In addition, preferred glossiness is more than 80%.

In addition, glossiness with the vertical direction of rolling direction on the normal reflection rate that benchmark is obtained that is defined as of JIS Z8741-1997 " method 360 degree specular glosss ".

＜anodic oxidation treatment 〉

As anodic oxidation treatment, can use present known method.Specifically, preferably use own regularization method described later.

Thereby own regularization method is the regular method of important factor raising of utilizing the character of the micropore rule arrangement of anodic oxidation coating, confusing the rule arrangement by eliminating.Specifically, use raffinal, utilize the voltage corresponding with the kind of electrolytic solution, cost long-time (for example from several hours to tens hours), low speed ground form anodic oxidation coating.

Representation example as own regularization, known have a J.Electrochem.Soc.Vol.144, No.5, May 1997, p.L128 (non-patent literature 7), Jpn.J.Appl.Phys.Vol.35 (1996) Pt.2, No.1B, L126 (non-patent literature 8), Appl.Phys.Lett, Vol.71, No.19,10 Nov1997, p.2771 (non-patent literature 9), above-mentioned non-patent literature 1.

The technical characterictic of the method for putting down in writing in these known documents is, uses high purity material, with the specific voltage corresponding with electrolytic solution, implements long time treatment with lower temperature.Specifically, use the above material of any aluminium purity 99.99 quality %,, carry out own regularization method with the condition shown in following.

(0.3mol/L mol) sulfuric acid, 0 ℃, 27V, 450 minutes (non-patent literature 7)

0.3mol/L sulfuric acid, 10 ℃, 25V, 750 minutes (non-patent literature 7)

0.3mol/L oxalic acid, 17 ℃, 40～60V, 600 minutes (non-patent literature 8)

0.04mol/L oxalic acid, 3 ℃, 80V, thickness 3 μ m (non-patent literature 9)

0.3mol/L phosphoric acid, 0 ℃, 195V, 960 minutes (non-patent literature 9)

The own regularization anodic oxidation treatment of Shi Yonging for example can be used the method for switching on as anode with aluminium base in the solution of acid concentration 1～10 quality % in the present invention.As the solution that in anodic oxidation treatment, uses, can use oxalic acid, sulfuric acid, citric acid, propanedioic acid, tartrate, phosphoric acid etc. separately or be used in combination more than 2 kinds.

Owing to by the electrolytic solution that uses, the condition of own regularization anodic oxidation treatment various variations takes place, and can not generally determine, but general preferred concentration of electrolyte is 0.01～10mol/L, 0～20 ℃ of solution temperature, current density 0.1～10A/dm ², voltage 15～240V, electric weight 3～10000C/dm ², electrolysis time 30～1000 minutes.

Electrolysis is preferably carries out the constant voltage electrolysis.

The proterties of anodic oxidation coating is as follows.

When containing the blocking layer, thickness is preferably more than the 0.1 μ m, more preferably more than the 1 μ m.In the time of in above-mentioned scope, it is better that the regularity of micropore becomes.

In addition, when containing the blocking layer, thickness is preferably below 100 μ m.In the time of in above-mentioned scope, in stripping process described later, peel off from aluminium base easily.

Preferably below 600nm, more preferably 5～400nm especially is preferably 10～80nm to the thickness on blocking layer.In the time of in above-mentioned scope, the separability excellence in the aftermentioned stripping process.

The aperture is 10～500nm, is preferably 15～100nm, more preferably 20～80nm.In the time of in above-mentioned scope, during filler metal, filled with metal gets more even in micropore.

The coefficient of variation in aperture is not particularly limited, preferably less than 30%, and more preferably 5～20%.

The coefficient of variation in aperture (CV:Coefficient of Variation) is the dispersive index in aperture, is defined by following formula.

(coefficient of variation in aperture)=(standard deviation in aperture)/(mean pore size)

The cycle of micropore is preferably 20～700nm, more preferably 25～600nm, most preferably 25～150nm.

In addition, the coefficient of variation in micropore cycle is not particularly limited, preferably less than 30%, more preferably more than 5% and less than 20%.

The area occupation ratio that micropore occupies is preferably 10～70%.

The wide processing in＜hole 〉

In the present invention, above-mentioned aluminium parts also can be the parts that the antianode oxide film thereon has been implemented the wide processing in hole.

The wide processing in hole is such processing: after anodic oxidation treatment, by aluminium base is immersed in acidic aqueous solution or the alkaline aqueous solution, dissolve anodic oxidation coating, enlarge the aperture of micropore.Thus, just control the regularity that micropore is arranged easily.

In the wide processing in hole, use under the situation of acidic aqueous solution, preferably use the aqueous solution of mineral acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or their mixture.The concentration of acidic aqueous solution is preferably 1～10 quality %.The temperature of acidic aqueous solution is preferably 25～40 ℃.

In the wide processing in hole, use under the situation of alkaline aqueous solution, preferably use at least a alkaline aqueous solution of from the group that constitutes by sodium hydroxide, potassium hydroxide and lithium hydroxide, selecting.The concentration of alkaline aqueous solution is preferably 0.1～5 quality %.The temperature of alkaline aqueous solution is preferably 20～35 ℃.

Specifically, for example, preferably use 50g/L, 40 ℃ phosphate aqueous solution, 0.5g/L, 30 ℃ aqueous sodium hydroxide solution or 0.5g/L, 30 ℃ potassium hydroxide aqueous solution.

The time of flooding in acidic aqueous solution or alkaline aqueous solution is preferably 8～60 minutes, and more preferably 10～50 minutes, especially preferred 15～30 minutes.

＜blocking layer thin layer processing 〉

In the present invention, above-mentioned aluminium parts be make the change of anodic oxidation coating thin layer aluminium parts, be one of preferred state.During the blocking layer thin layer, separability becomes excellent in stripping process described later.

The inventor finds, after anodic oxidation, voltage is not sharply changed, but reduce voltage gradually, that is, do not produce electric current time of recovery, while the method that the state that keeps making electric current keep flow state usually descends voltage, just can not damage the regularity of the micropore arrangement of anodic oxidation coating, can make the blocking layer thin layerization of anodic oxidation coating.This is to consider owing to do not produce electric current time of recovery, so can not cause fine branch.

Specifically, for example, the voltage of anodic oxidation treatment is under the situation more than the 100V, and the speed that voltage descends was preferably below 20V/ minute, more preferably below 10V/ minute, especially was preferably below 5V/ minute.

Keep the big fashion of electric current.Specifically, preferred 10 μ A/cm ²More than, more preferably 30 μ A/cm ²More than, especially preferred 50 μ A/cm ²More than.

Electric current is crossed when low because that micropore is arranged is regular chaotic, therefore with above-mentioned speed, electric current less than 10 μ A/cm ²Situation under, preferably once ending voltage and descending, electric current is with 10 μ A/cm by the time ²When more than flowing, just continue to make voltage to descend.

＜other processing 〉

In addition, as required, can carry out other processing.

For example, structure of the present invention is placed on the sample table, the aqueous solution that drips becomes under the membranaceous situation it, in order to reduce the contact angle of structure and water, also can implement hydrophilic treatment.Can implement hydrophilicity-imparting treatment by existing known method.

In addition, structure of the present invention is placed on the sample table, with acid to its modification or make under the situation of protein as object of its decomposition, in and in anodic oxidation treatment, use, in the acid of aluminium remained on surface, can also implement neutralizing treatment.Can implement neutralizing treatment by existing known method.

＜stripping process 〉

Stripping process is to peel off above-mentioned anodic oxidation coating and above-mentioned aluminium base by above-mentioned aluminium parts is carried out electrolysis as negative electrode, obtains the operation of the structure that is made of anodic oxidation coating.In addition, in stripping process, aluminium parts is carried out electrolysis as negative electrode, but because this electrolysis with this anodic oxidation treatment is opposite as the anodic situation with aluminium parts, thus below be called " against electrolysis ".

In stripping process, by this contrary electrolysis, at the anodic oxidation coating of aluminium parts and the hydrogen of generation at the interface of aluminium base, by hydrogen reduction, dissolved the part of the part that is connected with the aluminium base on the blocking layer at the interface that is in anodic oxidation coating and aluminium base, make it become aluminum ion, so think that anodic oxidation coating separates at it at the interface with aluminium base.

In contrary electrolysis, as negative electrode, use above-mentioned aluminium parts, make electric current flow through the surface of anodic oxidation coating, so implement electrolysis.Like this, will peel off easily.

Wherein, preferably make electric current only flow through the surface of anodic oxidation coating, implement electrolysis.That is, preferred electric current flows through the surface of anodic oxidation coating, and does not flow through electric current on the aluminium base of aluminium parts, so implements electrolysis.

Specifically, for example, electrolytic solution is contacted with the surface of anodic oxidation coating, making electrolytic solution not contact the side of anodic oxidation coating and the state enforcement electrolysis down of aluminium base simultaneously.So the method for state is not particularly limited, for example, can enumerate the surface of using mask or anchor clamps to expose anodic oxidation coating only after, the method for dipping aluminium parts in electrolytic solution, only method of electrolyte is supplied with on the surface of antianode oxide film thereon.

Use the method for mask by cover part outside the part that contacts with the electrolytic solution on the anodic oxidation coating surface of aluminium parts with insulating material.

As insulating material, be not particularly limited, be 10 preferably 20 ℃ of lower volume resistivity ¹⁶The material that Ω m is above.For example, can enumerate resin (natural resin and synthetic resins), rubber, pottery (for example glass), metal oxide, mica.

Wherein, preferred soft synthetic resin.As synthetic resins, can enumerate vinylchlorid, polycarbonate, vinylformic acid, PET, Resins, epoxy, polyimide, polypropylene, polyester, polyethylene, silane, the inferior ethene of polychlorostyrene.

Also can suitably use the insulating tape (below be called " splicing tape ") that has applied caking agent with these synthetic resins as base material.As splicing tape, for example, (for example can enumerate epoxy resin film, the Super10 of 3M corporate system), polyimide film (for example, 1205 of the 3M corporate system), PTFE film (for example, 62 of the 3M corporate system), polyester film are (for example, the 3M corporate system 56), the plastic film band (for example, scotch tape 470, the 3S corporate system), polyester film (for example, Japanese electrician makes the ェ レ ッ プ mask N-300 of society's system), polypropylene screen (for example, Japanese electrician makes the sodium salicylate ダ Application プ ロ Application of society's system).

Do not limit the method for utilizing insulating material to cover especially, for example, under the situation of using resin, can enumerate the method for the aqueous resin of coating (for example tamanori), paste the method for splicing tape.In addition, for example, can be according to the part that covers, and the back side that is used in aluminium base pastes after the splicing tape, applies these methods such as aqueous resin in the side of aluminium base and anodic oxidation coating.

Wherein, paste the method for the resinous belt applied caking agent owing to insulativity in the electrolytic solution, set about and easy these points of method easily, so carry out preferred.

The thickness of the insulating material of cover part, on this aspect of electrical insulating property preferably more than 1 μ m, 10～200 μ m more preferably on this aspect of operability.

Under the situation of adhesive-applying on the insulating material and tamanori, the coating homogeneity and prevent that their thickness is preferably 10～100 μ m on these aspects of bonding after strain.

As mentioned above, by cover with insulating material except that with part that the electrolytic solution on the anodic oxidation coating surface of aluminium parts contacts part carry out mask.Specifically, cover the whole of the side of anodic oxidation coating and aluminium base with insulating material.

At this, also can cover the part of anodic oxidation coating.In this case, peeling off easily on this aspect, the afterwards residual peristome of a part that preferably covers anodic oxidation coating is circular, oval, round rectangle.Wherein, by carrying out the whole surface of contrary electrolytic part, can evenly carry out on contrary this aspect of electrolysis circular.

Do not limit the method for using anchor clamps especially, expose the only method of the anchor clamps on the surface of anodic oxidation coating even if use.

The anode that uses in contrary electrolysis is not particularly limited, and for example, can list Ti electrode, Pt electrode, the carbon dioxide process carbon electrode of plating Pt.

The electrolytic solution that uses in contrary electrolysis is not particularly limited the preferred acidic aqueous solution.

Acidic aqueous solution is preferably pH 1～7, and more preferably pH 2～6, especially preferred pH 2.5～5.5.In addition, the specific conductivity of acidic aqueous solution is 0.01～100mS/cm, more preferably 0.1～50mS/cm.

The pH of acidic aqueous solution and specific conductivity are difficult to produce the corrosion and the residual film of aluminium base when above-mentioned scope, separability is good.

The specific conductivity of acidic aqueous solution is crossed when hanging down, and the mnm. of current value can not take place.In this case, the ionic concn in the acidic aqueous solution is uprised, the mnm. of current value takes place.On the contrary, during acidic aqueous solution intermediate ion excessive concentration,, also stop in the short period of time even if the mnm. of current value takes place, thereafter, because current value can sharply increase the difficulty so control becomes.Further, when surpassing when reaching minimizing time, will corrode.

In the acidic aqueous solution,, can suitably use oxalic acid, sulfuric acid, phosphoric acid as acid.

In addition, for example, can use and be dissolved in demonstration tart metal chloride in the water, be dissolved in demonstration tart organic compound in the water.

Show the tart metal chloride in the water as being dissolved in, for example, can enumerate oxalic acid aluminium, Tai-Ace S 150, Aluctyl, aluminum fluoride, aluminum borate.

Be dissolved in and show tart organic compound optimization acid in the water, for example, can suitably list the aromatic hydroxy-carboxylics such as aromatic binary carboxylic acids such as aromatic series monocarboxylic acid, phthalic acid, Whitfield's ointment such as unsaturated aliphatic di-carboxylic acid, M-nitro benzoic acid such as representative examples of saturated aliphatic di-carboxylic acid, toxilic acid of hexanodioic acid.

In addition, can use be dissolved in the water show neutral salt, be neutral salt.As neutral salt, for example, can suitably list the borate such as carbonate, ammonium borate of volatile salt etc.

Use under the situation of neutral salt, further, as additive, for the mixed solution that has added fluorochemical, carbonic acid dielectric medium or acid amides also is one of preferred form.As fluorochemical, can enumerate Neutral ammonium fluoride.As the carbonic acid dielectric medium, for example can enumerate Guanidinium carbonate, urea, formaldehyde.As acid amides, for example can enumerate ethanamide.

In the middle of them, preferred oxalic acid, oxalic acid aluminium, sulfuric acid, Tai-Ace S 150 or their mixture.Particularly, preferably sulfuric acid aluminium, sulfuric acid on chirality and these aspects of liquid waste disposal.

In addition, the preferred use kind identical with the electrolytic solution that uses in above-mentioned anodic oxidation treatment also is one of form.

Owing to contrary electrolytic condition is carried out various variations according to employed electrolytic solution, so can not generally determine.

For example, be 0.4～10 quality % during the preferred oxalic acid aqueous solution of the concentration of electrolytic solution, during aqueous sulfuric acid 2～20 quality %, during phosphate aqueous solution 0.4～5 quality %.

The temperature of electrolytic solution is preferably 0～50 ℃ usually, more preferably 10～35 ℃.

Current density is preferably 1～400mA/dm ², 5～400mA/dm more preferably ², most preferably be 10～300mA/dm ²When above-mentioned scope, peel off Shi Buhui and take place randomly, can carry out more equably.

Voltage is preferably 5～350V, more preferably 8～300V, most preferably 10～240V.Electrolysis voltage when the preferred voltage ratio forms anodic oxidation coating is lower.

In addition, voltage fixedly is one of preferred form, and it also is one of preferred implementation that voltage rises in time.

In the present invention, preferably become 0.1A/dm at current value ²Finish electrolysis after the following moment.

Fig. 1 be expression with aluminium parts with aluminium base and anodic oxidation coating as negative electrode, make electric current only flow through the surface of anodic oxidation coating and the timeliness of implementing the electric current electrolytic the time changes schematic chart.

(T after the beginning electrolysis ₁) to T ₃Till, exist electric current to become the peaked moment (T ₂).At T ₁T ₃During this time, owing to observed the gas generation, be inferred as H in the interface generation of anodic oxidation coating and aluminium base ⁺, become hydrogen molecule by electrochemical reaction.

After this, at T ₄, electric current sharply descends, think at this moment and to carve, anodic oxidation coating and aluminium base peel off end.After this, at T ₅Before, it is constant still to keep low current value.At T ₄T ₅During this time, be speculated as between anodic oxidation coating and aluminium base, to accumulate hydrogen is arranged.

Then, when continuing, at T against electrolysis ₆Current value was once reaching peak value.Think that this is owing to produced crackle on anodic oxidation coating.

After this, at T ₇Afterwards, be speculated as the crackle of electrolytic solution by anodic oxidation coating and be penetrated between anodic oxidation coating and the aluminium base, corrode.

In the present invention, preferably at T ₄T ₅Finish electrolysis during this time.Thus, just can prevent the corrosion that the infiltration because of the crackle of anodic oxidation coating and electrolytic solution causes.For this reason, preferred monitor current value becomes 0.1A/dm at current value ²Finish electrolysis after the following moment.

Have again, at T ₄T ₅Current value during this time, with respect to its maximum value (at T ₂Constantly) usually below 30%, most below 10%.Therefore, the monitor current value, finishing electrolysis after current value becomes its peaked moment below 30% or below 10% also is one of preferred implementation.

The back side of aluminium base and side (edge section), in order to expose metallic aluminium, when not carrying out mask etc. since in metallic aluminium current concentration, electric current is difficult to flow to anodic oxidation coating, so peel off become difficulty, the homogeneity variation of release surface in addition.

In addition, when not carrying out mask, because most electric current flows through metallic aluminium, the difficulty so the state of peeling off of holding anodic oxidation coating according to the variation of current value becomes.As mentioned above, by utilizing insulating material to cover the side of anodic oxidation coating and the state of peeling off that whole aluminium base just can be held anodic oxidation coating according to the variation of current value.

Electrolysis for example, is just cut off and the anodic oxidation coating of peeling off can be separated with aluminium base by the intersection in part that flows through electric current and the part that does not flow through electric current after finishing.At this moment, the stress rupture anodic oxidation coating when cutting off in order not make is taken out after can be with splicing tape etc. fixing again.

In the aluminium base that the execution stripping process obtains, at the regional residual residue that anodic oxidation coating below the thickness 0.2 μ m is arranged below 10% of release surface.Utilizing under the situation of this aluminium base, preferably do not producing the residue of anodic oxidation coating.

Therefore, in the case, preferably after contrary electrolysis, carry out chemical treatment, remove the residue of anodic oxidation coating.Particularly, the aqueous solution by making various acidity or alkalescence and the chemical treatment (chemical grinding processing) of the contacted method of anodic oxidation coating etc. just can be removed.The method of chemical treatment (chemical grinding processing) does not limit especially, for example can use existing known method to carry out.

As acidic aqueous solution, for example can list the mixed aqueous solution of phosphate aqueous solution, aqueous sulfuric acid, aqueous nitric acid, the oxalic acid aqueous solution, chromic acid and phosphoric acid.Wherein, the mixed aqueous solution of preferred chromic acid and phosphoric acid.

Acidic aqueous solution, preferred pH-0.3～6, more preferably pH 0～4, and most preferably pH 2～4.

Preferred 20～60 ℃ of the temperature of acidic aqueous solution, more preferably 30～50 ℃.

Treatment time, preferred 1 second～6 hours, more preferably 5 seconds～3 hours, most preferably 10 seconds～1 hour.

As the water-soluble various aqueous solution that list sodium hydroxide, yellow soda ash, potassium hydroxide of alkalescence.

The preferred pH 10～13.5 of alkaline aqueous solution, more preferably pH 11～13.

Preferred 10～50 ℃ of the temperature of alkaline aqueous solution, more preferably 20～40 ℃.

Treatment time, preferred 1 second～10 minutes, more preferably 2 seconds～1 minute, most preferably 3 seconds～30 seconds.

In addition, can make up these methods.For example, can enumerate to carry out utilizes alkaline aqueous solution that the surface of aluminium base is dissolved slightly, remove after the basic treatment of residue of anodic oxidation coating, carry out utilize that acidic aqueous solution makes that basic treatment thus produces in and the method handled of resultant dissolving, the decontamination stain removed.

Particularly, for example, can enumerate to carry out contacting after the basic treatment of 5 quality % aqueous sodium hydroxide solutions (70 ℃ of temperature) for 10 seconds, carry out the method for the decontamination stain processing that contacts 30 quality % aqueous sulfuric acids (50 ℃ of temperature) 60 seconds.

In addition, for example list in " aluminum technology brief guide ", light metal association and compile the whole bag of tricks that (1996), カ ロ ス publish, p.926-929 put down in writing as the pre-treatment of chemistry in (non-patent literature 10).Wherein, can the give an example alkaline degreasing that preferably has the upper layer dissolved effect that makes aluminium base, sour degreasing, electrolytic degreasing, these combination, the alkali etching with the strong effect of the upper layer dissolved that makes aluminium base is handled, acid etching is handled, the combination of these processing.

In addition,, repeatedly carry out anodic oxidation treatment and lift-off processing operation, just can fully remove residual anodic oxidation coating by alternate repetition carrying out under the also a part of residual situation of stripping process anodic oxidation coating.

In this method, do not recover,, therefore in the 2nd embodiment of the present invention described later, carry out preferred so do not upset the regularity of arrangement of the pit of aluminium base side owing to do not carry out electric current when peeling off anodic oxidation coating.

Below, the example against electrolytic suitable condition is shown for example.

＜suitable condition 1 〉

Negative electrode: in the oxalic acid aqueous solution of 17 ℃ of concentration 0.3mol/L (mol), temperature, carry out anodic oxidation coating, thickness 60 μ m that anodic oxidation treatment obtains under voltage 40V, the condition in 60 minutes treatment times

Anode: carbon dioxide process carbon electrode

The aluminum sulfate aqueous solution that electrolytic solution: concentration 0.04g/L (aluminum ion conversion), pH 3.8, specific conductivity 0.6mS/cm, temperature are 33 ℃

Voltage: 40V (setting voltage)

In the 1st embodiment of the present invention, the treatment time of stripping process is than carry out dissolved demoulding operation weak point extremely of needed time in the mixed aqueous solution of existing chromic acid and phosphoric acid.Therefore, according to the 1st embodiment of the present invention, can carry out the manufacturing of effective structure.

And, the water mixed liquid of chromic acid and phosphoric acid, when degreasing process, the content of aluminum oxide is as Al ₂O ₃When surpassing 15g/L, because the dissolving power rapid deterioration just needs the new treatment solution of exchange.The common thickness of the anodic oxidation coating of Shi Yonging is thicker in the present invention, so it is big to dissolve the amount of the aluminum oxide that through primary treatment, the deterioration of treatment solution will be very rapid.

On the contrary, in the present invention, owing to peel off anodic oxidation coating at the interface of anodic oxidation coating and aluminium base with solid-state form, so can utilize strainer etc. to separate easily, the acidic aqueous solution that uses in contrary electrolysis can deterioration.

Therefore the consumption of the treatment time of the stripping process among the present invention and acidic aqueous solution will be lacked and considerably less than the consumption of treatment time of the demoulding operation of existing mixed aqueous solution by chromic acid and phosphoric acid and treatment solution very much.

In stripping process, by above-mentioned contrary electrolysis, make the blocking layer dissolving, obtain the structure that constitutes by anodic oxidation coating.

In addition, on the other hand, peeled off the aluminium base of anodic oxidation coating, become aluminium base with a plurality of pits.Aluminium base with these a plurality of pits can be used for the 2nd embodiment of the present invention described later.Use accompanying drawing to specifically describe below.

Fig. 2 is the explanatory view of the manufacture method of structure of the present invention.

Fig. 2 (A) is the schematic sectional view of the green parts before the stripping process.Shown in Fig. 2 (A), aluminium parts 10 comprises: aluminium base 12, be present in the lip-deep anodic oxidation coating 14 of aluminium base 12.Have micropore 16 in anodic oxidation coating 14, its underpart becomes blocking layer 18.

Fig. 2 (B) and Fig. 2 (C) are respectively the structure that obtains by stripping process and the schematic sectional view of aluminium base.

The blocking layer 18 of the anodic oxidation coating 14 of the aluminium parts 10 shown in dissolving Fig. 2 (A) and obtain the structure 20 shown in Fig. 2 (B), it is made of the anodic oxidation coating with a plurality of pits 22.

The blocking layer 18 of the anodic oxidation coating 14 of the aluminium parts 10 shown in dissolving Fig. 2 (A) and obtain the aluminium base 24 shown in Fig. 2 (C), it has a plurality of pits 26.

The 2nd embodiment of the present invention is a kind of manufacture method of structure, comprise: the aluminium parts by the anodic oxidation coating that will have aluminium base and exist on above-mentioned aluminium base surface is implemented electrolysis as negative electrode, peel off above-mentioned anodic oxidation coating and above-mentioned aluminium base, obtain the stripping process of the structure that constitutes by aluminium base with a plurality of pits; Aluminium base with above-mentioned a plurality of pits is implemented anodic oxidation treatment, obtain the anodic oxidation treatment operation of the structure that constitutes by the aluminium base that has the anodic oxidation coating that has micropore on the surface; Wherein, in above-mentioned stripping process, implement above-mentioned electrolysis according to the mode that makes electric current only flow through the surface of above-mentioned anodic oxidation coating.

Carry out the stripping process of the 2nd embodiment of the present invention in the same manner with the stripping process of the 1st embodiment of the present invention.

＜anodic oxidation treatment operation 〉

In the 2nd form of the present invention, behind stripping process, carry out the anodic oxidation treatment operation.

The anodic oxidation treatment operation is that the aluminium base with a plurality of pits that is obtained by stripping process is implemented anodic oxidation treatment, obtains the operation of the structure that is made of the aluminium base that has the anodic oxidation coating that has micropore on the surface.

In the aluminium base with a plurality of little holes that stripping process obtains, the bottom shape on the blocking layer of the micropore that rule is arranged becomes the pit (with reference to Fig. 2 (C)) on surface.Therefore, this surperficial pit almost is hemispherical, is similarly arranging regularly with micropore.

The anodic oxidation treatment operation can be used existing known method.Anodic oxidation treatment during particularly, with the above-mentioned aluminium parts of acquisition is identical.

At this, the electrolytic solution of the electrolytic solution identical type of using and using in above-mentioned contrary electrolysis is one of preferred implementation.Thus, in same electrolyzer, just can carry out contrary electrolysis and anodic oxidation treatment operation.In addition, even when using another electrolyzer to carry out, can not produce bad influence because of electrolytic solution being brought into the anodic oxidation treatment groove yet.

In this anodic oxidation treatment operation, a plurality of pits that aluminium base surface rule is arranged are the starting point of anodic oxidation treatment, form the anolyte and the tunicle of the micropore with rule arrangement.

Therefore, utilize the structure that constitute of anodic oxidation treatment operation acquisition by the aluminium base of the anodic oxidation coating that has the micropore that has the rule arrangement on the surface.

Fig. 2 (D) is the schematic sectional view by the structure that obtains of anodic oxidation treatment operation.By being implemented anodic oxidation treatment formation anodic oxidation coating 30, the aluminium base shown in Fig. 2 (C) 24 obtains the structure 28 shown in Fig. 2 (D).During anodic oxidation treatment, be that starting point forms micropore 32 with the pit 26 of aluminium base 24.Therefore, structure 28 constitutes by have the aluminium base 34 that has anodic oxidation coating 30 on the surface.

In the 2nd embodiment of the present invention, the treatment time of stripping process with in the mixed aqueous solution of existing chromic acid and phosphoric acid, carry out the needed time of dissolved demoulding operation and compare remarkable weak point.Therefore, according to the 2nd embodiment of the present invention, just can carry out the manufacturing of effective structure.

＜chemical dissolution treatment process 〉

In the 2nd embodiment of the present invention, also be included in after the above-mentioned anodic oxidation treatment operation, the chemical dissolution treatment process of the structure that is made of the aluminium base that has the anodic oxidation coating that has micropore on the surface being implemented the chemical dissolution processing is one of preferred implementation.By carrying out the chemical dissolution treatment process, make the aperture more even.

Can adopt with the wide processing in above-mentioned hole just as method carry out chemical dissolution and handle.

＜structure 〉

The structure that constitutes by anodic oxidation coating that obtains by the present invention's the 1st embodiment and by the present invention's the 2nd embodiment obtain by have the structure that the aluminium base that has micropore constitutes on the surface, have a plurality of pits and the micropore that rule is arranged owing to have any one, so can be applied to various uses.

For example, handle,, just can use with sample table etc. as Raman's spectrum analysis by filler metal in a plurality of pits or micropore through sealing of hole.

In addition, can use with mould as nano print.

And the structure that is made of anodic oxidation coating that obtains by the 1st embodiment of the present invention can use as separator-filter.

＜sealing of hole is handled 〉

It is the element that is made of the metallic bond with unbound electron that sealing of hole is handled employed metal, though do not limit especially, preferably can confirm the metal of plasma unit resonance.Wherein, known gold and silver, copper, nickel, platinum cause plasma unit resonance easily, so carry out preferred (at modern chemistry, in September, 2003 number, p.20～27 (non-patent literature 11)).Especially, preferably carry out the gold and silver that electrodeposit and colloidal particle are made easily.

The method that sealing of hole is handled does not limit especially, can adopt existing known method.

For example, the dispersion liquid that electrodeposit method can suitably be enumerated structure metallizing colloidal particle of the present invention makes its exsiccant method.Metal is single particle or aggregate preferably.

The electrodeposit method can adopt existing known method.Particularly, for example can enumerate under the situation of golden electrodeposit method, aluminium parts is immersed in contain the HAuCl of 1g/L ₄H with 7g/L ₂SO ₄30 ℃ of dispersion liquids in, under the constant voltage (adjusting) of 11V, carry out the method that electrodeposit in 5～6 minutes is handled with slidac.

As the electrodeposit method, at modern chemistry, in January, 1997 number, p.51-54 write up the example that uses copper, tin and nickel in (non-patent literature 12), also can use this method.

Can be by have the dispersion liquid that the known method acquisition is used now in the method for using the metallic colloid particle.The metallic colloid particle making method of atomic making method that for example, can be by utilizing the rough vacuum method of evaporation, the aqueous solution of reducing metal salt obtains.

Preferred its median size of metallic colloid particle is 1～200nm, more preferably 1～100nm, most preferably 2～80nm.

As the dispersed catalyst that in dispersion liquid, uses, preferably make water.In addition, can also use and mix the solvent that obtains, for example alcohol of ethanol, n-n-propyl alcohol, i-propyl alcohol, 1-butanols, 2-butanols, t-butanols, methylcyclohexane (メ チ Le ャ Le ソ Le Block), ethylene glycol butyl ether (Block チ Le ャ Le ソ Le Block) etc. and the mixed solvent of water with water.

In the method for using the metallic colloid particle, do not limit coating method especially, for example, can enumerate tower coating, spin coated, spraying, the coating of curtain formula, dip coating, air-blade type coating, scraper-type coating, roller coating etc.

Dispersion liquid as using in the method for using the metallic colloid particle for example can suitably use gold colloid dispersion of particles liquid, silver colloid dispersion of particles liquid.

As gold colloid dispersion of particles liquid, for example can use the spy and open flat 2001-89140 communique and the special dispersion liquid of putting down in writing in the flat 11-80647 communique of opening.In addition, also can use the market sale product.

As silver colloid dispersion of particles liquid, be not subjected to preferably to contain the particle of the alloy of silver and palladium from the influencing on this aspect of the acid of anodic oxidation coating stripping.In the case, preferred 5～30 quality % of the amount of palladium.

Behind the coating dispersion liquid, the water equal solvent is suitably cleaned.Thus, can the residual particle that only is filled in a plurality of pits or the micropore, remove the particle that is not filled in a plurality of pits or the micropore.

Metal adhesion amount after sealing of hole is handled is preferably at 100～500mg/m ²

In addition, the surface void rate after sealing of hole is handled is preferably below 20%.Surface void rate after sealing of hole is handled is the overall proportion with respect to the area of the peristome of a plurality of pits of the not sealing of hole of the area on structure surface or micropore.The surface void rate can obtain the first resonance of stronger local plasma when above-mentioned scope.

The method of using the metallic colloid particle can suitably be adopted in the aperture when 50nm is above.In addition, during less than 50nm, preferably use the electrodeposit method in the aperture.Also can suitably use the method that makes up the above two.

Structure after sealing of hole is handled, because of the metal sealing of hole a plurality of pits or micropore, on the surface of structure, just have particle to exist.

In order to make Raman's reinforcing effect become big, lack at the interval of usually preferred this metallics, but best interval is subjected to the influence of the size and the shape of metallics.In addition, according to the molecular weight of the material of a corpse or other object for laboratory examination and chemical testing that becomes Raman's spectrum analysis and the viscosity of liquid, there is the situation of not going deep into the problem that waits between metallics well that produces.

Therefore, can not generally determine the interval of metallics, usually the scope of preferred 1～400nm, more preferably 5～300nm, most preferably 10～200nm.When above-mentioned scope, it is big that Raman's reinforcing effect becomes, and become such problem that the material of a corpse or other object for laboratory examination and chemical testing is not deep between metallics and will tail off.

At this, " interval of metallics " is the shortest distance on the surface of the particle that is adjacent to each other.

The caused Raman's reinforcing effect of＜local plasma unit's resonance 〉

Raman's reinforcing effect is the Raman scattering intensity enhancing 10 of the adsorbed molecule of metal ⁵～10 ⁶Phenomenon doubly is called as the surface and strengthens resonance Raman scattering (SERRS:Surface EnhancedResonance Raman Scattering) phenomenon.And, in above-mentioned non-patent literature 11, record situation by means of the local plasma resonance acquisition Raman of the unit reinforced effects of the metallics that uses gold and silver, copper, platinum, nickel etc.

Than prior art, because the structure of sealing of hole after handling can produce the big local plasma unit resonance of intensity, so when being used for Raman's spectrum analysis, will obtain stronger Raman's reinforcing effect.Therefore, it is useful using Raman's spectrum analysis sample table of the structure after sealing of hole is handled.

Use the using method of Raman's spectrum analysis of the structure after sealing of hole is handled with sample table, identical with existing Raman's spectrum analysis with the using method of sample table.Particularly,, measure the light of reflection or the Raman scattering intensity of the light that sees through, detect near the characteristic of the material the metal of sample table maintenance thus using Raman's beam split sample table irradiates light of the structure after sealing of hole is handled.

＜nano print 〉

Structure of the present invention can use with mould as nano print.Particularly, solidify in a plurality of pits by making inflow structures of the present invention such as resin or the micropore, just can access substrate with a plurality of thrusts.Have the substrate of these a plurality of thrusts, for example can be used in the optics.

(embodiment)

Show embodiment below, specifically describe the present invention.But, the invention is not restricted to this.

1, the making of structure

(embodiment 1～15 and comparative example 1)

The substrate order is implemented polished finish, the processing of own regularization, mask and contrary electrolysis, obtain the structure and the aluminium base that constitute by anodic oxidation coating.The aluminium base that obtains is implemented the wide processing of this anodic oxidation treatment and hole in proper order, obtain the structure that constitutes by aluminium base.

Explaining each below handles.

(1) substrate

Substrate 1 below when the making of structure, using.

Substrate 1: the pure pharmaceutical worker's industry of raffinal and light society system, purity 99.99 quality %, thickness 0.4mm

(2) polished finish

Aforesaid substrate is implemented following polished finish.

＜mirror polish is handled 〉

Implement the mirror polish processing by grinding.Use the electrolytic solution (65 ℃ of temperature) of following compositions, establishing anode is substrate, and negative electrode is a carbon dioxide process carbon electrode, at 12.5A/dm ²Constant current under, carry out 5 minutes electrolytic polishings.

＜bath composition 〉

85 quality % phosphoric acid (with the system reagent of the pure pharmaceutical worker's industry of light society) 1320mL

50 quality % aqueous sulfuric acid 600mL

Pure water 20mL

(3) own regularization anodic oxidation treatment (formation of pit)

Own regularization anodic oxidation treatment is implemented on any one surface to the substrate of having implemented mirror process according to following condition A and condition B, forms pit.This pit becomes the starting point that micropore forms in described later anodic oxidation treatment.

＜own regularization anodizing 〉

＜condition A 〉

Use sulfuric acid (the system reagent of Northeast chemistry society), the aqueous sulfuric acid that modulation concentration 0.3mol/L, temperature are 16 ℃.(treatment zone 5cm * 10cm) be immersed in this aqueous sulfuric acid under the constant voltage condition of voltage 25V, carries out 7 hours own regularization anodic oxidation treatment, forms the anodic oxidation coating of thickness 90 μ m on substrate to make substrate.

In own regularization anodic oxidation treatment, use the SUS304 electrode, use NeoCool BD36 (ャ マ ト science society system), use double stirrer PS-100 (EYELA society system), use GP0650-2R (high sand is made society of institute system) as power supply as stirring warming apparatus as refrigerating unit as negative electrode.Have again, the face of not relative with the electrode surface of substrate side is not implemented anodic oxidation treatment, paste PET band (sodium salicylate adhesive tape, day eastern electrician's system) in advance.

＜condition B 〉

Use oxalic acid hydrogen peroxide (two water and thing) (the system reagent of Northeast chemistry society), the oxalic acid aqueous solution that modulation concentration 0.5mol/L, temperature are 16 ℃.(treatment zone 5cm * 10cm) be immersed in this oxalic acid aqueous solution under the constant voltage condition of voltage 40V, carries out 5 hours own regularization anodic oxidation treatment, forms the anodic oxidation coating of thickness 45 μ m on substrate to make substrate.

In own regularization anodic oxidation treatment, use the SUS304 electrode, use NeoCool BD36 (ャ マ ト science society system), use double stirrer PS-100 (EYELA society system), use GP0650-2R (high sand is made society of institute system) as power supply as stirring warming apparatus as refrigerating unit as negative electrode.Have again, the face of not relative with the electrode surface of substrate side is not implemented anodic oxidation treatment, paste PET band (sodium salicylate adhesive tape, day eastern electrician's system) in advance.

＜film thickness measuring method 〉

Be bent to form the substrate of anodic oxidation coating,, use super-resolution ability type SEM (S-900 of Hitachi, Hitachi's system), under acceleration voltage 20V, observe for 200 times, measure thickness with multiplying power at the side (ruptured surface) of the part that cracks.Randomly draw 10 positions each time and ask its mean value, be made as thickness.The value of the thickness at 10 positions is in the scope of mean value arbitrarily ± 10%.

(4) mask

The substrate of implementing own regularization anodic oxidation treatment is carried out mask.The method of mask is shown in the 1st table.The meaning of the mark in the 1st table is as follows.

" nothing ": after the own regularization anodic oxidation treatment, divest the PET band, do not carry out mask and supply with contrary electrolysis.

" back side ": after the own regularization anodic oxidation treatment, still keep the PET band, supply with contrary electrolysis.

" back side+edge ": after the own regularization anodic oxidation treatment, still keep the PET band, and apply 2 liquid mixed type Resins, epoxy (epoxy resin binder, ニ ヂ バ Application (strain) buy) in the substrate end, leave standstill 1 angel's hardening of resin after, supply with contrary electrolysis.

" back side+edge+surfaces A ": after carrying out above-mentioned " back side+edge " processing, paste the PET band (sodium salicylate band, day eastern electrician's system) of circular open further on the surface of anodic oxidation coating side with radius 1.7cm.Have again, paste the PET adhesive tape, make its opening be located substantially on the central authorities of substrate, and cover the substrate end sclerosis resin.

" back side+edge+surperficial B ": after carrying out above-mentioned " back side+edge " processing, paste the PET band (sodium salicylate band, day eastern electrician's system) of elliptical openings further on the surface of anodic oxidation coating side with major diameter 2.5cm, minor axis 1.4cm.Have again, paste the PET adhesive tape, make its opening be located substantially on the central authorities of substrate, and cover the substrate end sclerosis resin.

" back side+edge+surface C ": carry out after above-mentioned " back side+edge " handle, the PET band (sodium salicylate band, day eastern electrician's system) of opening of the round dot of radius 5mm is set near pasting the foursquare summit that has at a slice 3cm on the surface of anodic oxidation coating side further.Have again, paste the PET adhesive tape, make its opening be located substantially on the central authorities of substrate, and cover the substrate end sclerosis resin.

" back side+edge+surperficial D ": after carrying out above-mentioned " back side+edge " processing, paste the PET band (sodium salicylate band, day eastern electrician's system) of foursquare opening further on the surface of anodic oxidation coating side with a slice 3cm.Have again, paste the PET adhesive tape, make its opening be located substantially on the central authorities of substrate, and cover the substrate end sclerosis resin.

" special fixtures ": as shown in Figure 3, in anodic oxidation coating 14 sides of the aluminium base 12 (aluminium parts 10) that forms anodic oxidation coating 14, the configuration special fixtures is supplied with contrary electrolysis.Special fixtures have negative electrode 40, internal space have negative electrode 40 encapsulation 42, be arranged on electrolyte stream inlet 44 and electrolyte stream outlet 46 in the encapsulation.Negative electrode 40 diameters are 3cm.Its diameter of internal space of encapsulation 42 is that 3cm, the degree of depth are 2cm.The reverse checkvalve (not shown) of double as pressure valve is set in electrolyte stream outlet 46.During contrary electrolysis, (use shadow representation by electrolyte stream 44 electrolytic solution that enter the mouth.) can flow in the encapsulation 42, exporting 46 electrolytic solution from the internal space 42 that encapsulates by electrolyte stream can flow out, in addition, for not making end and the anodic oxidation coating 14 of electrolyte leakage, become above state by encapsulation being pressed on encapsulation 42 on the anodic oxidation coating 14.Have, Fig. 3 is the schematic explanatory view of employed special fixtures in the contrary electrolysis again, and with respect to the size of special fixtures, the size of micropore 16 is different with reality.

(5) contrary electrolysis

After carrying out mask, use the substrate formed above-mentioned anodic oxidation coating as negative electrode, use the Pt electrode, in the aluminum sulfate aqueous solution of 33 ℃ of concentration 4.5g/L, temperature as anode, under the constant voltage condition of voltage 16V, carry out contrary electrolysis, anodic oxidation coating and aluminium base are peeled off.The substrate that has formed anodic oxidation coating is a vertical direction by the face direction of substrate, is configured in the aluminum sulfate aqueous solution.

In contrary electrolysis, carry out the monitoring of current value.Current value when the maximum value of current value shown in the 1st table, contrary electrolysis end and current ratio (maximum value of the current value/current value when contrary electrolysis finishes).

Having, in embodiment 15, is not constant voltage again, with lift velocity 2V/ minute, voltage is increased from 0V to 17.8V point-blank gradually, carry out contrary electrolysis (in the 1st table, do not put down in writing the maximum value and the current ratio of current value.)。

After contrary electrolysis finishes, on the surface of anodic oxidation coating, paste PET band (sodium salicylate band, day eastern electrician's system), after this, in contrary electrolysis, cut otch with cutter, anodic oxidation coating is separated with aluminium base at the intersection of part that contacts with electrolytic solution and discontiguous part.

(6) this anodic oxidation treatment

Implement this anodic oxidation treatment in contrary electrolysis, peeling off the aluminium base that anodic oxidation coating obtains.Except that the treatment time is 2 minutes, by with own regularization anodic oxidation treatment in the identical condition A or the B that use carry out this anodic oxidation treatment.

(7) the wide processing in hole

In order to improve the homogeneity that sealing of hole described later is handled, the aluminium base after this anodic oxidation treatment is implemented the wide processing in hole.By making aluminium base be immersed in the phosphate aqueous solution (30 ℃ of temperature) of concentration 5 quality % 15 minutes, carry out the wide processing in hole.

2, peel off the evaluation of state

The anodic oxidation coating after the contrary electrolysis in the evaluation the various embodiments described above and the state of peeling off of aluminium base.

Particularly, to the release surface of the aluminium base after the contrary electrolysis, by visual, be coated with the white dark part of full no specular gloss with pen, by image analysis, calculating has the area occupation ratio of the part of specular gloss, thus the homogeneity peeled off of evaluation.

The result is shown in the 1st table.In the table, for " homogeneity of peeling off ", represent to have the area occupation ratio of the part of specular gloss to surpass 95% with A, be lower than 100% situation, represent to surpass 90%, be lower than 95% situation with B, represent to surpass 85%, be lower than 90% situation with C, represent to surpass 80%, be lower than 85% situation with D, represent to surpass 70%, be lower than 80% situation, represent to be lower than 70% situation with F with E.

3, the evaluation of the structure that constitutes by aluminium base

Find the solution the regularization degree as the index of the regularity of micropore of aluminium base after this anodic oxidation treatment.The result is shown in the 1st table.

Have, the regularization degree defines by following formula (1) again.

Regularization degree (%)=B/A * 100 (1)

At this, in above-mentioned formula (1), A represents the quantity of all micropores in the useful range.B represents that with the center of a micropore (center of gravity) be the center, receives the shortest bowlder of radius at the edge of another micropore in depicting, and contains the center of 6 above-mentioned micropores micropore in addition in the inside of this circle

Quantity in the useful range of the previous micropore of (center of gravity).

Fig. 4 is the explanatory view of method that calculates the regularization degree in hole.Use Fig. 4 to be described more specifically above-mentioned formula (1).

Micropore 1 shown in Fig. 4 (A) is the center at the center (center of gravity) with micropore 1, when receiving the shortest circle 3 of the radius at edge of another micropore in depicting (in be connected on micropore 2), comprises the center (center of gravity) of 6 micropores except that micropore 1 in the inside of circle 3.Therefore, micropore 1 is counted B.Micropore 4 shown in Fig. 4 (B) is the center at the center (center of gravity) with micropore 4, when receiving the shortest circle 6 of the radius at edge of another micropore in depicting (in be connected on micropore 5), comprises the center (center of gravity) of 5 micropores except that micropore 4 in the inside of circle 6.Therefore, micropore 4 is not counted B.In addition, micropore 7 shown in Fig. 4 (B), at the center (center of gravity) with micropore 7 is the center, when receiving the shortest circle 9 of the radius at edge of another micropore in depicting (in be connected on micropore 8), comprises the center (center of gravity) of 7 micropores except that micropore 7 in the inside of circle 9.Therefore, micropore 7 is not counted B.

Table 1

	Own regularization anodic oxidation treatment condition	Mask method	Contrary electrolysis voltage (V)	Maximum value (the mA/dm of current value 2)	Current value (mA/dm when contrary electrolysis finishes 2)	Current ratio (%)	The homogeneity of peeling off	Regularization degree (%)
									Comparative example	A	Do not have	25	500	500	100	F	-
Embodiment 1	A	The back side	25	300	200	67	E	50
									Embodiment 2	A	The back side+edge	25	250	60	24	C	50
Embodiment 3	A	The back side+edge	25	250	100	40	D	50
									Embodiment 4	A	The back side+edge	25	250	150	60	E	50
Embodiment 5	A	The back side+edge+surfaces A	25	250	60	24	A	70
									Embodiment 6	A	The back side+edge+surperficial B	25	250	60	24	A	60
Embodiment 7	A	The back side+edge+surface C	25	250	60	24	B	50
									Embodiment 8	A	The back side+edge+surperficial D	25	250	60	24	C	50
Embodiment 9	A	The back side+edge+surfaces A	20	250	20	8	C	50
									Embodiment 10	A	The back side+edge+surfaces A	18	250	20	8	B	60
Embodiment 11	A	The back side+edge+surfaces A	15	250	30	12	A	70
									Embodiment 12	A	The back side+edge+surfaces A	13	250	50	20	E	60
Embodiment 13	B	The back side+edge+surfaces A	40	250	60	24	A	70
									Embodiment 14	A	Special fixtures	25	250	60	24	A	70
Embodiment 15	A	The back side+edge+surfaces A	0→17.8	-	30	-	A	50

As indicated in table 1, the manufacture method of structure of the present invention (embodiment 1～15), the homogeneity that any one is peeled off and obtained constitute the regularity in the hole of structure all good by aluminium base.

With respect to this, make electric current flow through aluminium base and carry out under the contrary electrolytic situation (comparative example), the homogeneity of peeling off is deterioration then.

Claims (11)

1, a kind of manufacture method of structure, comprise: the aluminium parts by the anodic oxidation coating that will have aluminium base and exist on above-mentioned aluminium base surface is implemented electrolysis as negative electrode, above-mentioned anodic oxidation coating and above-mentioned aluminium base are peeled off, obtained the stripping process of the structure that constitutes by anodic oxidation coating; Wherein,

In above-mentioned stripping process, implement above-mentioned electrolysis according to the mode that makes electric current flow through the surface of above-mentioned anodic oxidation coating.

2, the manufacture method of structure according to claim 1 in above-mentioned stripping process, is implemented above-mentioned electrolysis according to the mode that makes electric current only flow through the surface of above-mentioned anodic oxidation coating.

3, the manufacture method of structure according to claim 2, in above-mentioned stripping process, make electrolytic solution contact the surface of above-mentioned anodic oxidation coating, simultaneously electrolytic solution contacted under the state of the side of above-mentioned anodic oxidation coating and above-mentioned aluminium base to implement above-mentioned electrolysis.

4 manufacture method according to any described structure in the claim 1～3 in above-mentioned stripping process, become 0.1A/dm at current value ²After the following time point, finish above-mentioned electrolysis.

5, a kind of structure that manufacture method obtained that requires any described structure in 1～4 by aforesaid right.

6, a kind of manufacture method of structure, comprise: implement electrolysis by the aluminium parts of the anodic oxidation coating that will have aluminium base and on above-mentioned aluminium base surface, exist as negative electrode above-mentioned anodic oxidation coating and above-mentioned aluminium base are peeled off, obtain the stripping process of the structure that constitutes by aluminium base with a plurality of pits;

Aluminium base with above-mentioned a plurality of pits is implemented anodic oxidation treatment, obtain the anodic oxidation treatment operation of the structure that constitutes by the aluminium base that has the anodic oxidation coating that has micropore on the surface; Wherein,

In above-mentioned stripping process, implement above-mentioned electrolysis according to the mode that makes electric current flow through the surface of above-mentioned anodic oxidation coating.

7, the manufacture method of structure according to claim 6 in above-mentioned stripping process, is implemented above-mentioned electrolysis according to the mode that makes electric current only flow through the surface of above-mentioned anodic oxidation coating.

8, according to the manufacture method of the structure described in the claim 7, in above-mentioned stripping process, make electrolytic solution contact the surface of above-mentioned anodic oxidation coating, simultaneously electrolytic solution contacted under the state of the side of above-mentioned anodic oxidation coating and above-mentioned aluminium base to implement above-mentioned stripping process.

9, according to the manufacture method of any described structure in the claim 6～8, in above-mentioned stripping process, become 0.1A/dm at current value ²After the following time point, finish above-mentioned electrolysis.

10, according to the manufacture method of any described structure in the claim 6～9, also comprise: after above-mentioned anodic oxidation treatment operation, the structure that is made of the aluminium base that has the anodic oxidation coating that has above-mentioned micropore on the surface is implemented the chemical dissolution treatment process that chemical dissolution is handled.

11, a kind of structure that manufacture method obtained by any described structure in the claim 6～10.

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