CN108330523A - The method for quickly forming surface plasma sub-structure - Google Patents
The method for quickly forming surface plasma sub-structure Download PDFInfo
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- CN108330523A CN108330523A CN201810118509.4A CN201810118509A CN108330523A CN 108330523 A CN108330523 A CN 108330523A CN 201810118509 A CN201810118509 A CN 201810118509A CN 108330523 A CN108330523 A CN 108330523A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
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Abstract
The present invention proposes a kind of method forming surface plasma sub-structure comprising：One base material is provided；And anode processing is carried out in an alkaline electrolysis confrontation base material, so that a surface of base material is reacted into plasma-based sub-structure.It, can be in substrate surface be reacted into plasma-based sub-structure in the short time by the method.
Description
Technical field
The present invention relates to a kind of methods forming surface plasma sub-structure, and quickly forming surface particularly with regard to a kind of
The method of plasma-based sub-structure.
Background technology
Color comes from paint pigment, bioluminescence or structure.Structural color is mainly by the week of light and nanostructure
Caused by effect between phase arrangement, it includes interference (interference), diffraction (diffraction), scatterings
(scattering) or RESONANCE ABSORPTION (resonance absorption).Thus, which electromagnetic wave can be caused in specific light wave
Long lower reflection.According to the viewpoint of biology, the regional areas of many species has structural color, as peacock tail, butterfly's wing,
The blade of Selaginella flora, the thorn of sea caterpillar, these regions have 1D, 2D or 3D arrangement of nanostructure (also known as
Make " photonic crystal ").In addition, it has been found that the periodic nano-structure to many types can provide structural color, such as multilayer, hole
Hole, groove, grating, hemisphere, nano particle of different shapes.
With aforementioned electromagnetic wave structure act on similar physical mechanism earliest by Wood in 1902 propose (see
Philosophical Magazine Series 4 (1902) 396), and the wave that he notes abnormalities in Metal diffraction grating spreads out
It penetrates.Caused by later, this exception of Fano and Hessel propositions resonates for propagation plane wave with material surface (see
J.Opt.Soc.Am.31(1941)213、Appl.Opt.4(1965)1275).It is connect once incident electromagnetic wave enters metal-dielectric
When mouth (including vacuum), no proximity mouth electrons generate polarization charge in metal surface, and cause set eelctric dipole oscillation.It is this
Solid-state material characteristic can use plasma-based conceptual description at surface plasma sub-resonance.It is dissipated extensively using surface-enhanced Raman by the seventies
After penetrating (surface enhanced Raman scattering, SERS), surface plasma sub-resonance science has developed in last decade
For crucial and widely acquisition research and application；Moreover, several the relevant technologies and product, such as the sub- sensor of plasma-based, nano impression,
It has come into being.
Plasma-based minor structure coloration material has many advantages, as color filter, colored printing, and can be applied to display skill
Art.Its value has attracted many research interests, especially its light characteristic, such as color saturation, incidence angle, corresponding receives
Rice structure.Plasma-based minor structure coloration material obtains in a variety of nanometers of arrangement architectures, including hole, particle, grating or gold
The structures such as category-dielectric-metal.However, it is well known that compared to the metal column, hole and reguline metal of nanoscale, nanometer ruler
Lower offer absorption maximum rate can be grown in the arrangement in dielectric body in Different lightwave by spending metal hemisphere.Especially, vacuum deposition
The cost and complexity of the made nano particle of system are quite high.
Anodised aluminium processing is a kind of method of the antivacuum manufacture structural color film of surface plasmon.Growth-erosion
Three step process of quarter-growth can produce high order hexagonal lattice structure.In addition, the voltage bestowed, current-mode, electrolyte are dense
Degree, the bore hole size that anodic aluminum oxide film can be precisely controlled with parameters such as solution temperatures.But in most cases, in acidity
The pore space structure that the nanoscale of author's preface is manufactured in solution is unfavorable, because comparing fine and close and plane anodic oxidation aluminized coating
Manufacture, need be up to a few hours to a few days processing time.
Invention content
The purpose of the present invention is to solve the problems, such as to commonly use the spent overlong time of anode processing.
Then, to solve the above problems, the present invention proposes a kind of method forming surface plasma sub-structure comprising：
One base material is provided；And anode processing is carried out in an alkaline electrolysis confrontation base material, so that a surface of base material is reacted into plasma-based sub- knot
Structure layer.
In an embodiment, the base material is a metal base.
In an embodiment, the base material is one containing aluminium base.
In an embodiment, the base material is an aluminum alloy base material.
In an embodiment, the plasma-based sub-structure is a γ-Al2O3Layer.
In an embodiment, the alkaline electrolyte is the electrolyte of an acid group containing silicon and phosphate radical.
In an embodiment, the alkaline electrolyte contains KOH, Na4P2O7·10H2O, and Na2SiO3。
In an embodiment, the pH of the alkaline electrolyte is 10 to 14.
In an embodiment, anode processing uses direct current power mode.
In an embodiment, anode processing bestows 7.5 to 40mAcm-2Current density.
In an embodiment, the method further includes：A metal layer is formed on a surface of plasma-based sub-structure.
To sum up, compared to carried out under acidic electrolyte bath anode processing, this method can quickly by substrate surface react at
Plasma-based sub-structure.
Description of the drawings
Figure 1A is photo figure, shows the appearance of metal-dielectric-metal structure.
Figure 1B is CIE1931 chromaticity coordinate figures, confirms the reflection color of metal-dielectric-metal structure.
M- voltage relationship figure when Fig. 2 is illustrates to bestow voltage corresponding under different current densities.
Fig. 3 is scanning electron microscope photo figure, and the anodised aluminium painting for bestowing gained under different current densities is presented
The cross-section structure of layer.
Fig. 4 is scanning electron microscope photo figure, and the anodised aluminium painting for bestowing gained under different current densities is presented
The appearance of layer.
Fig. 5 is X-ray scattering technology result figure, illustrates the composition of anodic oxidation aluminized coating.
Fig. 6 A are to illustrate the characteristic of anodic oxidation aluminized coating using the full rate complexity figure obtained by electrochemical impedance spectroscopy.
Fig. 6 B are to illustrate the characteristic of anodic oxidation aluminized coating using the Bode diagram obtained by electrochemical impedance spectroscopy.
Fig. 6 C are to utilize the frequency 10 obtained by electrochemical impedance spectroscopy5To the multiple plan views of Nyquist impedances of 400Hz,
Illustrate the characteristic of anodic oxidation aluminized coating.
Fig. 7 A are ultraviolet light wave band Luminance Analysis result figure, illustrate the reflected light wavelength of anodic oxidation aluminized coating.
Fig. 7 B are visible light wave range Luminance Analysis result figure, illustrate the reflected light wavelength of anodic oxidation aluminized coating.
Fig. 8 is ultraviolet light wave band Luminance Analysis result figure, illustrates the reflected light wavelength of metal-dielectric-metal structure.
Fig. 9 is visible light wave range Luminance Analysis result figure, illustrates the reflected light wavelength of metal-dielectric-metal structure.
Figure 10 is CIE1931 chromaticity coordinate figures, confirms the reflection of the metal-dielectric-metal structure of different gold plating thickness
Color.
Specific implementation mode
To allow the above-mentioned and/or other purposes of the present invention, effect, feature to be clearer and more comprehensible, preferred embodiment cited below particularly is made
It is described in detail：
＜ experimental examples ＞
One, the pre-treatment of aluminium sample
Select 6061 aluminium alloys of AA as base material with low cost because widely using.Aluminium sample is cut into 20x20mm pieces
Body, and all surface is ground with about 0.1 μm of center line average roughness (Ra).Then, M3x0.5 is dug out with screw thread
Hole and connect with aluminium alloy wire to guarantee well to be electrically connected between power supply unit.Finally, it is gone with ultrasonic vibrating
Its spot is removed except residual object in al alloy specimens, and with the deionized water of room temperature and acetone.
Two, it is handled in acid containing silicon and phosphoric acid electrolyte Anodic
Using the 5L stainless steel sinks configured with cooling and stirring system as counter electrode, and electrolyte temperature maintains about 25
℃.Al alloy specimens are fixed on centre to ensure that electric field is evenly distributed in two main visible surfaces.Then, in alkaline electrolysis
Anode processing is carried out to completely ground al alloy specimens (surface area 1,600mm2) in matter (pH12), and electrolyte contains 1g/L
KOH、2g/L Na4P2O7·10H2O, and 2g/L Na2SiO3.Each anodised aluminium processing is carried out using direct current power mode, and
Electric current is bestowed under this pattern about 1 minute, it is 7.5 to 40mAcm to continue the current density bestowed in period-2。
Three, it post-processes
Using sputtering way bestow a gold plating on the surface that anodised aluminium was handled with for surface plasma sub-resonance
Metal-dielectric-metal sandwich structure is produced, sputter deposition rate is about 0.35nm/s；In addition, this mode can form outer gold
Belong to layer.The another influence for the outer metal layer thickness of research to surface plasma sub-resonance, coating time are 10 to 40 seconds.
Four, specificity analysis
The table of plasma-based minor structure color sample is analyzed with Flied emission scanning electron microscope (S-4800, Hitachi)
Face exterior appearance and feature.Separately use energy dispersion X-ray spectrum (energy dispersive X-ray
Spectroscopy the composition of anodic oxidation aluminized coating) is measured.Further to study the cross-section structure of anodic oxidation aluminized coating, in
The above-mentioned experiment of repetitive operation is to measure anodised aluminium coating layer thickness on the closed aluminium-foil paper of 2x2mm and one end.It later, will be remaining
Base material be dipped in copper chloride solution (13.5g is dissolved in 100mL hydrogen chloride) to remove it.Then, then with Flied emission scan-type
Electron-microscopic analysis removes the exterior appearance of processed anodic oxidation aluminized coating.Another aspect, passes through because of palpus conduction state
Scanning electron microscope studies appearance of coat pattern, and the sample of all preparations must be coated with gold about 20 seconds.X-ray is selected to scatter skill
Art (0.1 degree of glancing angle) confirms the composition for being formed by film.Finally, electrochemical impedance spectroscopy is utilized
(electrochemical impedance spectroscopy, EIS) further appreciates that anodic oxidation aluminized coating in deionization
Characteristic in water.This Systematic selection platinum line is with commercially available silver/silver chloride electrode respectively as counter electrode and reference electrode.To ensure
System is stablized, and before carrying out electrochemical impedance spectroscopy analysis, each sample is dipped in deionized water about 5 minutes.
Utilize ultraviolet-visible (UV-VIS) spectrophotometric (UV-1601, Shimadzu Scientific
Instruments plasma-based minor structure colored coatings) are analyzed, this can be shown in different current densities and be reflected under gold plating thickness
The reaction of light.To make comparisons, the sample of untreated al alloy specimens and only gold plating is separately used.Finally, using coloration
(X-rite S60, Torso-Verlag) is counted to confirm the color of each sample according to CIE color space chromacity diagrams.
＜ analyzes example ＞
After preparing plasma-based minor structure colored coatings, 10 samples for bestowing different current densities are taken further to study, such as
Figure 1A is it can be seen that have：(1) different to show color area (7.5mAcm-2It is blue region down；12mA·cm-2Lower is green
(dark blue) region；13mA·cm-2It is yellow area down；21mA·cm-2It is red area down；30mA·cm-2It is purple area down
Domain)；(2) similar to show color area (15mAcm-2Lower is golden yellow region)；(3) by red to purple color transfer (21 to
23mA·cm-2Under)；(4) color area (the 35 and 40mAcm repeated-2Lower is respectively blue and green area).According to
20 seconds golden sample colors are bestowed made by CIE1931 chromaticity coordinates confirms such as Figure 1B.It is apparent that reflection color is complete in chromatography
Site preparation shifts clockwise.
To further discuss influence of the metal-dielectric-metal structure to reflection color, according to anodised aluminium coating characteristic
It influences and sample is divided into two groups by the influence of external gold plating thickness.It is total that still detailed research structure characteristic influences surface plasmon
The mechanism shaken.
One, the color appearance that dielectric-metal architectural characteristic is influenced
Fig. 2 is illustrated in the voltage instantaneous variation being recorded under the different current densities of all anodised aluminium processing.Such as
The anode process flow of general current control, short linear region are found in initial period, this can lead to faraday's reaction
(Faradaic reaction).Bestowing for high current density can cause high corresponding voltage.Such as table 1, when the current density bestowed
From 7.5mAcm-2To 40mAcm-2When, final voltage can dramatically increase (from 83.5V to 245.4V).This result illustrates that height is applied
It gives and thick anodic oxidation aluminized coating can be obtained under conditions of current density, and thickness can be from profile scanning formula electronics shown in Fig. 3
Microscope calculates.In particular, 40mAcm-2The sample thickness of lower gained is 7.5mAcm-23 times of lower gained person.Moreover,
Thickness (the R in a linear relationship of the current density and anodic coating that are applied2=0.91).In addition, the theoretic throat of anodic coating
It can be calculated by following formula in accordance with Faraday's law：
Wherein, I represents electric current, and t represents the duration of anode processing, and A represents the atomic wts of unit mole, and n is represented
The reaction of atomic valence of unit mole, F represent Faraday constant, and rho represents aluminium density, and S represents the surface area of base material.Compare experiment
As a result, it can be seen that coating formation efficiency (1 being shown in Table, from 66% to 35%) can be reduced under height bestows current density.This phenomenon can
It can be construed to betide caused by dielectric anode layer reacts with the bilayer (electric double layer, diffusion layer) at the interface between electrolyte.Moreover, figure
2 also confirm that anode processing reaction non-faraday reaction.
Table 1
Fig. 4 shows the appearance of anodic oxidation aluminized coating.With regard to 22mAcm-2For, local roughness region is apparent
's.Same phenomenon also sees 30 and 35mAcm-2Under conditions of.Energy-dispersive spectroscopy analysis result is shown in local roughness area
Silicon acid concentration (about 1.5at.%) in domain is about 2 to 3 times (being shown in Table 1) for (being less than 0.8at.%) in general plane region.Therefore
This region shows the relatively high silicon acid in anodised aluminium processing and participates in oxidation rate.The protrusion observed under all conditions
Place has confirmed that as silicon acid-aluminium-oxide crystalline phase.Furthermore the linear change of aluminium/oxygen ratio is by the nanometer ruler of anodic oxidation aluminized coating
It spends caused by thickness, and X-ray can penetrate these coatings.When anodic oxidation aluminized coating increases, come from aluminum alloy base material
Signal it is weaker.
On the other hand, it is seen that some wavelength size hole hole, but it is only limitted to 7.5 and 12mAcm-2Under conditions of gained
Sample.The main cause of hole is formed during handling aluminium anodes as mechanical pressure and electric-field enhancing type electrochemical reaction, and hole
Hole forms while having anode layer to be formed dissolves with oxide.Compared to acid solution, the Al in weakly acidic pH or alkaline solution2O3's
Dissolve relatively slow, this means the rare hole structure under neutral or alkaline environment.In in this case, hole still may occur in which in
The region of low mechanical strength is such as scraped at injury, impure place or tomography.It is considerable when compared with the hole in the arrangement of author's preface hole
It observes in 7.5mAcm-2Under conditions of gained sample in hole be distributed in like slot region, and in 12mAcm-2Condition
The more random distribution of sample Hole of lower gained.However, in bestowing under high current density, the aluminium ion given up can get enough energy
Amount is reacted with OH- to fill up hole.The reason of here it is anodic coating is without hole formation under high current density, also for 12 with
13mA·cm-2Under conditions of the insignificant reason of thickness.Furthermore bore hole size is between 10 to 50nm (tables 1).To 35mAcm-2
Under conditions of gained sample for, many holes (about 20nm) can be seen in local roughness region.Although without substantive hole type
At, but 35 and 40mAcm-2Under conditions of gained sample reflection color and 7.5 and 12mAcm-2Under conditions of gained sample
This is close.In addition, it is only related and unrelated with composition with structure for the color that confirmatory sample is presented, it is analyzed with X-ray scattering technology
7.5,22 and 40mAcm-2Under conditions of gained sample.As the result of Fig. 5 shows that the group of these anodised aluminiums becomes γ-
Al2O3。
The characteristic of anodic oxidation aluminized coating is further studied using electrochemical impedance spectroscopy.Such as Fig. 6 A, final frequency spectrum is divided into
Half-circle area (105 to 400Hz) and curve regions (400 to 10Hz), expression connect between anodic oxidation aluminized coating and coating/solution
There is electronics transfer between mouthful.According to surface and section pattern, two kinds of equivalent circuits are designed；Wherein, design have the circuits R-CPE with
The circuit of Warburg elements supplies 7.5 and 12mAcm-2Under conditions of gained sample, and have the circuits R-C and R-CPEdlIt returns
The circuit on road supplies the sample of gained under the conditions of remaining.
The multiple plan views of Nyquist impedances (Fig. 6 C) according to frequency spectrum half-circle area and spectrum amplitude known to Bode diagram (Fig. 6 B)
It is larger in thick coating.13 and 23mAcm-2Under conditions of gained sample respectively relatively it is expected greatly with it is small.This phenomenon may be attributed to
Coating layer thickness and appearance.Moreover, as shown in table 1 and scanning electron microscope photo figure, 13mAcm-2Under conditions of
Available most thin, the most fine and close and coarse less oxide layer of anodised aluminium processing.According to following formula, capacitance variations can be shown
The thickness (d) of coating and surface area (A) characteristic：
It is apparent that 13mAcm-2Under conditions of gained sample the circuits R-C high resistance and high capacitance can be provided.It reviews,
23mA·cm-2Under conditions of gained sample form small spectrum amplitude, this may be coating layer thickness it is relatively thick caused by；This coating
Only compared with 40mAcm-2Under conditions of gained coating it is thin.
To study from nanometer anodic oxidation aluminized coating in the surface plasmon of the dielectric-metal structure on aluminum alloy base material
Resonance, with UV-vis spectroscopy Luminance Analysis reflected light wavelength.The result of ultraviolet light wave band and visible light wave range each takes in figure
7A and 7B.Compared to blank sample (simple aluminum alloy base material), tool gold plating is in the sample on aluminum alloy base material in ultraviolet light wave
Section has two or three apparent reflection at peak, these wave crests also to see anodic oxidation aluminized coating.In addition, in carrying out anodized aluminum
It is relatively broad under these spikes Duan Yuchang optical wavelength and forward to the right displacement when increasing bestowed current density when reason；
Similar situation also sees visible light wave range.But relative to tool gold plating in the sample on aluminum alloy base material, reflected intensity is weaker
And across wider wave band, therefore plasma-based sub-resonance occurs only at coating/substrate interface.
In summary as a result, understanding that the parameter changed during anodised aluminium is handled can (such as the current density bestowed)
Forward direction influences the resonant wavelength of coating/base material interface.Moreover, most data show that the reflection color of dielectric-metal structure is special
Property is influenced by anodised aluminium coating layer thickness.In comparison, surface roughness can with the influence of silicon acid-aluminium-oxide high spot
Ignore.
Two, the color that outer metal layer influences is presented
When layer gold is deposited on anodic oxidation aluminized coating, it can substantially improve the characteristic that reflective color filters.In addition,
External coating thickness is also worth inquiring into the reaction of plasma-based sub-resonance.To ultraviolet light and visible light wave range, metal-dielectric-metal knot
Structure to the surface plasma sub-resonance of reflected waveband as shown in figs. 8 and 9.These figures show that outer metal layer can improve light absorption reaction,
And still control spectral peak wave band in ultraviolet light and visible light wave range Anodic Oxidation aluminized coating.
Especially for ultraviolet light wave band, under conditions of bestowing high current density, reflector space and absorption region it is mutual
It is higher to change frequency.In addition, influence of the outer metal layer to light absorption is negligible under the conditions of these figures are shown in majority.By ultraviolet light point
At ultraviolet light A (optical wavelength 315 to 400nm), ultraviolet B (optical wavelength 280 to 315nm), with ultraviolet light C (optical wavelength 100 to
280nm) discuss.For example, in bestowing current density 7.5mAcm-2Under conditions of, it can absorb most ultraviolet Bs；Instead
It, in bestowing current density 22mAcm-2Under conditions of, most ultraviolet Bs can be reflected.
Conversely, under visible light wave range, the influence that gold plating thickness reflects frequency spectrum is considered as, and this influences foundation
The characteristic slight variations of anodic oxidation aluminized coating.For example, to 7.5 and 12mAcm-2Under conditions of, the maximum of reflection at peak
Point is constant；However, when gold plating thickness increases, reflection narrows with absorption peak wave band.As shown in Figure 10, this result explanation
Sample is in 7.5mAcm-2Under conditions of will reflection color from blue purpling；Furthermore in 12mAcm-2Under conditions of color remain unchanged
Except being more saturated.This phenomenon may be to influence coating layer thickness with sedimentation time increase, to change gold plating characteristic.In turn
It says, to 13 and 15mAcm-2Under conditions of for, these variations are relatively dull：Gold plating makes reflection at peak narrow, and shows color
Color saturation degree increases.This may be because the natural colour of reflector space and gold overlaps.To 21mAcm-2Under conditions of and
Speech has minimum difference in optical band 400 to 520nm, but is greatly improved in other optical band albedoes and color is more full
With.To 22 to 40mAcm-2Under conditions of for, reflection characteristic and 12mAcm-2Under conditions of it is similar.With 40mAcm-2's
Under the conditions of for, color saturation correspond to increase.But influence of the gold plating characteristic changing to spectrum shift is significantly weak.
In summary as a result, although plasma-based sub-resonance betides the interface between gold/anodic oxidation aluminized coating of layer gold, altogether
Vibration wave length is determined by anodic oxidation aluminized coating.In addition, the characteristic of outer metal layer can substantially influence reflection and the absorption characteristic of structure.
Only as described above, only presently preferred embodiments of the present invention, but cannot be limited the scope of implementation of the present invention with this；
Therefore it is all according to simple equivalent change and modification made by scope of the present invention patent and description of the invention content, all still belong to this
In the protection domain of invention appended claims.
Claims (10)
1. a kind of method forming plasma-based sub-structure, which is characterized in that including：
One base material is provided；And
In an alkaline electrolysis verify the base material carry out anode processing, make the base material a surface react at the plasma-based sub-structure.
2. the method as described in claim 1, which is characterized in that the base material is one containing aluminium base.
3. the method as described in claim 1, which is characterized in that the base material is an aluminum alloy base material.
4. the method as described in claim 1, which is characterized in that the plasma-based sub-structure is a γ-Al2O3Layer.
5. the method as described in claim 1, which is characterized in that the alkaline electrolyte is the electrolysis of an acid group containing silicon and phosphate radical
Matter.
6. the method as described in claim 1, which is characterized in that the alkaline electrolyte contains KOH, Na4P2O7·10H2O, and
Na2SiO3。
7. the method as described in claim 1, which is characterized in that the pH of the alkaline electrolyte is 10 to 14.
8. the method as described in claim 1, which is characterized in that anode processing uses direct current power mode.
9. the method as described in claim 1, which is characterized in that anode processing bestows 7.5 to 40mAcm-2Electric current it is close
Degree.
10. the method as described in claim 1, which is characterized in that further include：
A metal layer is formed on a surface of the plasma-based sub-structure.
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Citations (3)
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|---|---|---|---|---|
| JP2005172569A (en) * | 2003-12-10 | 2005-06-30 | Fuji Photo Film Co Ltd | Fine structure, method for creating fine structure, and raman spectroscopy and spectroscope |
| CN101319994A (en) * | 2007-06-08 | 2008-12-10 | 富士胶片株式会社 | Microstructures, method for producing microstructures, and optical field amplifying device |
| CN101724880A (en) * | 2008-10-24 | 2010-06-09 | 比亚迪股份有限公司 | Electrolyte, anodization method and anodized silicon-aluminum alloy |
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2018
- 2018-02-06 CN CN201810118509.4A patent/CN108330523A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005172569A (en) * | 2003-12-10 | 2005-06-30 | Fuji Photo Film Co Ltd | Fine structure, method for creating fine structure, and raman spectroscopy and spectroscope |
| CN101319994A (en) * | 2007-06-08 | 2008-12-10 | 富士胶片株式会社 | Microstructures, method for producing microstructures, and optical field amplifying device |
| CN101724880A (en) * | 2008-10-24 | 2010-06-09 | 比亚迪股份有限公司 | Electrolyte, anodization method and anodized silicon-aluminum alloy |
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